The Effect of SiO2 Addition on the Grain Size and Photocatalytic Activity of TiO2 Thin Films

The uniform transparent TiO₂/SiO₂ nanometer composite thin films were prepared via sol-gel method on the soda lime glass substrates, and were characterized by X-ray photoelectron spectroscopy (XPS), FTIR spectroscopy, UV-VIS spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and BET surface areas. It was found that the addition of SiO₂ to TiO₂ thin films could suppress the grain growth of TiO₂ crystal and increase the hydroxyl content of the surface of TiO₂ films. The photocatalytic activity of the as-prepared TiO₂/SiO₂ composite thin films increases for SiO₂ content of less than 5 mol%.     

Effect of biphase on dielectric properties of Bi-doped lead strontium titanate thin films

Pb_0.4Sr_0.6TiO₃ (PST) thin films doped with various concentration of Bi were prepared by a sol-gel method. The phase status, surface morphology and dielectric properties of these thin films were measured by X-ray diffraction (XRD), scanning electron microscopy (SEM) and impedance analyzer, respectively. Results showed that the thin films with the maximum dielectric constant and minimum dielectric loss were obtained for x=0.15. For x<0.15, only pure PST perovskite phase were in the thin films. For 0.2<x<0.4, the PST/Bi₂Ti₂O₇ biphase were obtained. The thin films with pure Bi₂Ti₂O₇ pyrochlore phase were obtained for x=0.67. The biphase thin films had high tunability and high figure of merit (FOM). The FOM of PST/Bi₂Ti₂O₇ biphase thin film was about 6 times higher than that thin films formed with pure perovskite phase or pure pyrochlore phase.     

Photodegradation of Direct Blue-199 in carpet industry wastewater using iron-doped TiO2 nanoparticles and regenerated photocatalyst

Fe-doped TiO_2, Ti_1–xFe_xO₂ (x = 0.00, 0.02, 0.04, 0.06, 0.08, and 0.10), photocatalysts have been successfully synthesized via citric acid–assisted autocombustion method. The synthesized photocatalysts were characterized using different characterization techniques, such as X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), Fourier transform infrared (FT-IR), transmission electron microscopy (TEM), energy dispersive x-ray spectroscopy (EDX), and x-ray photoelectron spectroscopy (XPS). The XRD diffraction patterns revealed that synthesized photocatalysts have the anatase phase of TiO₂. The DRS analysis indicates a slight increment in absorbance in the visible light region by the Fe doping in TiO₂. The FT-IR spectra reveal the various stretching and bending vibrational bands of the Ti–O lattice. The XPS spectra confirm the presence of elements titanium, oxygen, and iron in the synthesized samples and determine binding energy of elements. TEM analysis shows the shape of the synthesized photocatalyst, and it was used to calculate the average particle sizes of undoped and Fe-doped TiO₂ (Ti_0.96Fe_0.04O₂) photocatalysts using a histogram. The photocatalytic activities of synthesized photocatalysts were determined by photodegradation of dye (Direct Blue 199), contaminating carpet industry wastewater in the photochemical reactor and open pan reactor. The maximum photodegradation activity was shown by the Ti_0.96Fe_0.04O₂ photocatalyst among all the synthesized undoped and Fe-doped photocatalysts. The synthesized photocatalyst (Ti_0.96Fe_0.04O₂) had better photocatalytic activity when compared to both, undoped TiO₂ and Aeroxide (Degussa) P-25. The used Fe-doped TiO₂ photocatalyst (Ti_0.96Fe_0.04O₂) was regenerated five times and investigated for its photocatalytic activity.     

Chemical solution processing and characterization of Ba(Zr,Ti)O<Subscript>3</Subscript>/LaNiO<Subscript>3</Subscript> layered thin films

Ba(Zr,Ti)O₃/LaNiO₃ layered thin films have been synthesized by chemical solution deposition (CSD) using metal-organic precursor solutions. Ba(Zr,Ti)O₃ thin films with smooth surface morphology and excellent dielectric properties were prepared on Pt/TiO _x /SiO₂/Si substrates by controlling the Zr/Ti ratios in Ba(Zr,Ti)O₃. Chemically derived LaNiO₃ thin films crystallized into the perovskite single phase and their conductivity was sufficiently high as a thin-film electrode. Ba(Zr,Ti)O₃/LaNiO₃ layered thin films of single phase perovskite were fabricated on SiO₂/Si and fused silica substrates. The dielectric constant of a Ba(Zr_0.2Ti_0.8)O₃ thin film prepared at 700°C on a LaNiO₃/fused silica substrate was found to be approximately 830 with a dielectric loss of 5% at 1 kHz and room temperature. Although the Ba(Zr_0.2Ti_0.8)O₃ thin film on the LaNiO₃/fused silica substrate showed a smaller dielectric constant than the Ba(Zr_0.2Ti_0.8)O₃ thin film on Pt/TiO _x /SiO₂/Si, small temperature dependence of dielectric constant was achieved over a wide temperature range. Furthermore, the fabrication of the Ba(Zr,Ti)O₃/LaNiO₃ films in alternate thin layers similar to a multilayer capacitor structure was performed by the same solution deposition process.     

Synthesis and characterization of Ti1−2xNbxNixO2−x/2 solid solutions

Doped-rutile has been traditionally used in ceramic pigments for its intense optical properties. In this paper, we compare the classical ceramic synthesis of Ti_1−2xNb_xNi_xO_2−x/2 system with the sol-gel methodology, which allows a reduction of the anatase-rutile transformation temperature. The composition was optimised in order to obtain a unique rutile phase with the minimum amount of pollutant Ni(II) and enhanced chromatic coordinates. Incorporation of the doping ions in the rutile structure was corroborated by XRD and Rietveld refinements. The species responsible for the colour mechanism were studied by different techniques. UV-VIS spectroscopy showed the characteristic features of Ni²⁺ ions, whose existence was corroborated by EPR and magnetic measurements. From these results, (Ni,Nb)doped-TiO₂ powder samples can be now shaped as thin films, monoliths, etc. by using sol-gel methodology without modifying their properties. This study introduces new possibilities of coloured TiO₂-based solid solutions in new combined advanced applications (colouring agent and photocatalyst, etc.).     

The effect of Sn dopant on crystal structure and photocatalytic behavior of nanostructured titania thin films

In this study, preparation of Sn doped (0–30 mol % Sn) TiO₂ dip-coated thin films on glazed porcelain substrates via sol–gel process have been investigated. The effects of Sn content on the structural, optical, and photo-catalytic properties of applied thin films have been studied by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), field emission SEM (FE-SEM), and high resolution transmission electron microscopy (HR-TEM). Surface topography and surface chemical state of thin films were examined by atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS). XRD patterns showed an increase in peak intensities of the rutile crystalline phase by increasing the Sn dopant. The prepared Sn-doped TiO₂ photo-catalyst films showed optical absorption edge in the visible light area and exhibited excellent photo-catalytic ability for degradation of methylene blue solution under UV irradiation. The result shows that doping an appropriate amount of Sn can effectively improve the photo-catalytic activity of TiO₂ thin films, and the optimum dopant amount is found to be 15 mol%. The Sn⁴⁺ dopants substituted Ti⁴⁺ in the lattice of TiO₂ and increased surface oxygen vacancies and the surface hydroxyl groups. TEM results showed small increase in planar spacing (was detected by HR-TEM caused by Sn dopants in titania based crystals).     

Improvement of the oxidation behavior of Ti1-xAlxN hard coatings by optimization of the Ti/Al ratio

The oxidation behavior of cubic Ti_1-xAl_xN films was improved by decreasing the Ti/Al ratio from 50/50 in the direction of the phase transition between cubic and hexagonal structure. Metastable, polycrystalline, single-phase Ti_1-xAl_xN films were deposited on high speed steel (HSS) substrates by reactive magnetron sputtering ion plating (MSIP). The composition of the bulk was determined by electron probe microanalysis (EPMA), the crystallographic structure by thin film X-ray diffraction (XRD). A Ti_1-xAl_xN film with a Ti/Al atomic ratio of 38/62 was deposited in cubic NaCl structure, whereas a further decrease of the Ti/Al ratio down to 27/73 led to a two-phase film with both cubic and hexagonal constituents. The Ti_0.38Al_0.62N film was oxidized in synthetic air for 1 h at 800?°C. The oxidic overlayer was analyzed by X-ray photoelectron spectroscopy (XPS) sputter depth profiling, EPMA crater edge linescan analysis, and secondary neutrals mass spectroscopy (SNMS). Scanning electron microscopy (SEM) micrographs of the cross sectional fracture were taken for morphological examination. With higher Ti content, the Ti_1-xAl_xN formed a TiO_2-x rich sublayer beneath an Al₂O₃ rich toplayer, whereas the oxide layer on the Ti_0.38Al_0.62N film consisted of pure Al₂O₃. The thickness of the oxide layer was determined to 60–80 nm, about a quarter of the oxide layer thickness detected on Ti_0.5Al_0.5N films. The absence of a TiO_2-x sublayer was also confirmed by XRD. The results show a distinct improvement of the oxidation resistance of cubic Ti_1-xAl_xN films by increasing the Al content from x = 0.5 to 0.62, whereas a further increase leads to the hexagonal structure, which is less suitable for tribological applications due to its tendency to form cracks during oxidation.     

NixCo3-xO4表面修饰对CdSe/TiO2纳米管阵列光电化学氧化水活性的影响

利用氨挥发诱导法在CdSe/TiO2纳米管阵列表面负载一层NixCo3-xO4。采用SEM、XRD、XPS、UV-Vis对样品进行表征,通过线性扫描伏安法测定光阳极的释氧电势来评价其光电水氧化活性。结果表明:表面NixCo3-xO4是尖晶石结构;相对于CdSe/TiO2纳米管阵列光阳极,NixCo3-xO4/CdSe/TiO2光阳极能将光电氧化水的过电势降低430 mV。Ni离子的引入使得NixCo3-xO4表面富含三价阳离子(Ni3+,Co3+),从而促进CdSe/TiO2光阳极光电水氧化的进行。     

室温下制备以{211}晶面为主的Ti1-xVxO2薄膜及其可见光催化性能

以金属Ti和V作为靶材,采用直流反应共溅射技术在室温下制备了以{211}晶面为主的锐钛矿相Ti_1-xV_xO₂薄膜,研究了不同V靶功率对Ti_1-xV_xO₂薄膜的薄膜成分、晶相结构和可见光催化性能的影响。研究表明,Ti_1-xV_xO₂薄膜的晶相结构为锐钛矿相,择优取向为(211),而结晶度受V靶功率的影响。随着V靶功率的增加,薄膜中V元素含量逐渐增加,同时,晶粒和沉积速率也逐渐增加。另外,当V靶功率为150W时,薄膜的表面粗糙度值有一个最大值。V的掺杂导致薄膜的能带间隙变窄,对光的吸收向可见光区偏移,从而有效地改善了薄膜的可见光催化能力。当V靶功率为150W时,Ti_1-xV_xO₂薄膜的能带间隙值为2.82eV,其在2h的可见光照射下分解了80%的RhB染料。这被归结于能带间隙窄,高能晶面{211}和结晶度高的共同作用。     

Powderless processing of ceramics: Thin-layer electroceramics

A review is made of progress on the sol-gel processing of dense insulating electroceramics by polymeric condensation routes. Up until the past ten years, powders and porous coatings were principally made for optical and conductive applications. Much effort was expended on silica (SiO₂) and silicate-based systems. Recently, these approaches have been extended to non-silicate systems [1]. In this paper information is presented for the powderless processing of selected electroceramics in thin-layer form. Materials include PbTiO₃, BaTiO₃, Ba_1–x Pb _x TiO₃, PbZrO₃, Pb(Zr_1–y Ti _y )O₃ and (Pb_1–x La _x )(Zr_1–y Ti _y )O₃ which find applications in ceramic capacitors, piezoelectric transducers and electrooptic modulators. The approach is to avoid powders, and the attendent problems of powder handling, flow, packing, etc., and make use of polymerization condensation reactions to form extended networks with chemical linkage. Data are reported for the synthesis and low temperature processing routes for amorphous and polycrystalline ceramics.     

Preparation and characterization of nanotube Li-Ti-O by molten salt method

Nanotube Li-Ti-O compound with high surface (198.6 m²·g⁻¹) was prepared by a method involving the treatment of nanotube Na₂Ti₂O₅·H₂O in molten LiNO₃ and characterization by means of transmission electron microscopy (TEM), energy-dispersive spectra (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and thermogravimetry-differential thermal analysis (TG/DTG). Results show that the nanotube Li-Ti-O compound prepared by this method involves two crystal phases: spinel Li₂Ti₂O₄ and anatase Li_xTiO₂ (x < 0.1). Li⁺ exhibits different Li1s binding energy in the two crystal phases. In ambient air, the Li-Ti-O compound adsorbs water easily, and the chemically adsorbed water is difficult to remove below 400°C. Translated from Chinese Journal of Inorganic Chemistry, 2006, 22(12): 2135–2139 [译自: 无机化学学报]     

Preparation and Photocatalytic Properties of Ti1-xZrxO2 Solid Solution

A series of Ti1-xZrxO2 materials were synthesized through a multistep sol-gel process. The structural characteristics were investigated using X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS） and Raman measurements. The experimental results showed that a solid solution could be obtained at low Zr/（Ti＋Zr） molar ratios （x ≤0.319）. Raman measurements exhibited that the presence of zirconium in the solid solutions greatly retarded the amorphous-anatase and anatase-rutile transitions. The diffuse reflectance UV-Vis spectra revealed that the bandgap of the solid solution was enlarged gradually with the increment of incorporated zirconium content. The Ti1-xZrxO2 solid solutions exhibited higher photocatalytic activity than pure TiO2 for the degradation of 4-chlorophenol aqueous solution.     

Preparation of Ba(Ti,Sn)O<Subscript>3</Subscript> thin films by PVP-assisted sol–gel method and their dielectric properties

Ba(Ti_1−x Sn _x )O₃ (x = 0.10 or 0.15) thin films were deposited on Si(100) and Pt(111)/TiO _x /SiO₂/Si(100) substrates via sol–gel spin-coating. Crack-free thin films could be obtained by single-step deposition, where the thickness was about 0.46 and 0.29 μm at 1000 and 2000 rpm, respectively. Circular delaminated parts 100 μm in diameter, however, tended to appear in thicker films deposited at 1000 rpm. On both kinds of substrates, the films were crystallized between 500 and 600 °C, where the perovskite phase emerged as the primary phase, and the formation of single-phase perovskite was basically achieved between 700–800 °C. The films deposited on Pt(111)/TiO _x /SiO₂/Si(100) substrates, however, tended to have small SnO₂ and BaCO₃ diffraction peaks, which decreased with increasing spinning rate. The dielectric properties were evaluated on the films deposited on Pt(111)/TiO _x /SiO₂/Si(100) substrates at 2000 rpm. The films prepared by single-step depositions had dielectric constants of 350 and 230, and dielectric loss of 0.30 and 0.10 at x = 0.1 and 0.15, respectively. The films prepared by two time deposition had dielectric constants of 450 and 250, and dielectric loss of 0.21 and 0.19 at x = 0.10 and 0.15, respectively.     

Textured PbTiO3, Pb(Ca)TiO3-Al2O3 Composite Films Prepared by Chemical Solution Deposition Method

Chemical solution deposition method (CSD) method was used to prepare PbTiO₃ (PT), Pb_{1– x} Ca _x TiO₃ (PCT), PbTiO₃-Al₂O₃ (PT-AL) and Pb_{1 – x} Ca _x TiO₃-Al₂O₃ (PCT-AL) thin films on amorphous (soda-lime glass, SiO₂ glass) substrates. The films were examined by XRD methods to describe the phase composition, cell parameters, type and degree of texture. In dependence on the molar ratio of Ti:Al, the different extent of crystallographic ordering was observed ranging from randomly oriented to strongly textured crystallites of PT. (100)uvw preferred orientation growth of PT grains was identified.     

三维有序结构In掺杂TiO_2薄膜的可见光催化活性

采用自组装生长聚苯乙烯胶体模板和溶胶-凝胶法,制备出三维(3D)有序结构In掺杂TiO2(IO-TiO2-In)薄膜可见光催化剂.光催化实验证明,IO-TiO2-In薄膜降解甲醛的可见光活性是TiO2和三维有序结构TiO2(IOTiO2)薄膜的5倍.利用X射线电子衍射(XRD)谱、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)和紫外-可见(UV-Vis)漫反射吸收光谱确定了催化剂的晶相结构、表面微结构和能带结构.结果表明,IO-TiO2-In薄膜具有锐钛矿型三维有序结构,与TiO2相比,增加了比表面积,提高光的利用率;掺入的In离子在薄膜表面形成In2O3和O-In-Clx(x=1,2)物种,既增强可见光的吸收,又有效地促进了光生载流子的分离,提高了光生载流子在固/气界面参加光催化反应的利用率,使催化剂的可见光催化活性显著提高.     

Fabrication and properties of xBiFeO3-(1 − x)Bi4Ti3O12 system by sol–gel process

The thin films of mixture of xBiFeO₃-(1 − x)Bi₄Ti₃O₁₂ (x = 0.4, 0.5, and 0.6) system were prepared by a sol–gel process. The thicknesses of the thin films were 540, 500, and 570 nm, respectively. The crystal structure of all thin films annealed at 650 °C was analyzed by X-ray diffraction. It was found that the thin films at x = 0.4 and 0.5 mainly consisted of a Bi₄Ti₃O₁₂ phase while Bi₅Ti₃FeO₁₅ was the major phase of the thin film at x = 0.6. The thin film (x = 0.6) showed better ferroelectric properties in remnant polarization and polarization fatigue than those observed in the thin films (x = 0.4 and 0.5). The values of remnant polarization 2P _r and coercive field 2E c of the thin film at x = 0.6 were 36 μC/cm² and 192 kV/cm at an applied electric field of 260 kV/cm, respectively. There was almost no polarization fatigue up to 10¹⁰ switching cycles. Also weak ferromagnetism was observed in the thin film at x = 0.6.     

Cu掺杂TiO_2薄膜的摩擦学性能

采用溶胶-凝胶法在普通玻璃基底上制备了纯TiO2和Cu掺杂的TiO2(Cu-TiO2)纳米结构薄膜,利用X射线光电子能谱(XPS)、原子力显微镜(AFM)、粉末X射线衍射(XRD)及UMT-3摩擦磨损试验机考察了Cu掺杂量对薄膜组成、结构、表面形貌及摩擦学性能的影响.结果表明,相比于纯TiO2薄膜,Cu掺杂TiO2纳米薄膜平整、均匀,具有较好的耐磨减摩性能.Cu掺杂量的多少直接影响Cu-TiO2薄膜的减摩抗磨性能,当Cu掺杂量为5%(摩尔分数)时,Cu-TiO2膜具有最佳的耐磨寿命和最低的摩擦系数.     

Preparation and characterization of thin TiO2-films on gold/mica

Flat and highly (111) oriented gold and silver films were prepared by physical vapour deposition (PVD) using optimized deposition parameters. On these films, which were characterized with atomic force microscopy (AFM), scanning tunneling microscopy (STM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), titanium dioxide films were deposited by electron beam evaporation and dip coating. Dip coating from titanium tetraisopropoxide solutions resulted in films with different morphology and coverage depending on the alkoxide concentration (0.009 mol/L – 0.60 mol/L) and the post-treatment. Scanning electron microscopy (SEM) and AFM revealed that the deposited TiO₂ consists of amorphous, highly porous islands when the applied alkoxide concentration is high (0.05 mol/L – 0.6 mol/L). At higher temperatures these amorphous TiO₂ islands sintered significantly and crystallized to anatase. In contrast, transparent TiO₂ films were obtained from low concentrated alkoxide solutions (< 0.01 mol/L) which covered the whole substrate, similar to electron beam evaporated thin films. Sputter profiles with ion scattering spectroscopy (ISS) indicated that the film thickness is in the range of 2 nm when alkoxide solutions with a concentration of 9 mmol/L are used. The deposition of TiO₂ by electron beam evaporation normally resulted in significantly reduced TiO₂ films, completely oxidized ones were obtained when deposition was performed at elevated oxygen partial pressures (p(O₂) > 2 × 10^–5 mbar).     

钛、铝和玻璃上TiO2光催化膜的失活研究

采用浸渍提拉法，在平行条件下制备了钛、铝和玻璃载体上的TiO₂膜TiO₂ / Ti、TiO₂ / Al和TiO₂ / G，利用X射线光电子能谱(XPS)、原子力显微镜(AFM)和光催化降解实验等手段对膜样品进行了表征和活性评价。实验结果表明，在铝和玻璃基材上制膜时发生了显著的基材元素溢出，使各膜样品的化学组成不同，同时TiO₂粒子和膜表面形貌也因前驱物烧结行为不同而差异较大。TiO_{2相似文献}   

XPS Analysis of Lead Zirconate Titanate Thin Films Prepared Via a Sol-Gel Process

The crystalline phase and composition of sol-gel-derived lead zirconate titanate (PbZr _x Ti_{1 – x} O₃, PZT) thin films were determined by an X-ray photoelectron spectroscopic (XPS) data processing technique. As a result, it was proved that existence of the surface layer with several tens nm in thickness, of which the crystalline phase and composition were different from those of the inside of the thin films, was found. The newly developed XPS analytical technique is much applicable for the characterization of PZT thin film surface.