Structural, optical and electrical characterization of spray-deposited TiO2 thin films

Titanium oxide (TiO₂) thin films were deposited onto glass substrates by means of spray pyrolysis method using methanolic titanyl acetyl acetonate as precursor solution. The thin films were deposited at three different temperatures namely 350, 400 and 450 °C. As-deposited thin films were amorphous having 100–300 nm thickness. The thin films were subsequently annealed at 500 °C in air for 2 h. Structural, optical and electrical properties of TiO₂ thin films have been studied. Polycrystalline thin films with rutile crystal structure, as evidenced from X-ray diffraction pattern, were obtained with major reflexion along (1 1 0). Surface morphology and growth stages based on atomic force microscopy measurements are discussed. Electrical properties have been studied by means of electrical resistivity and thermoelectric power measurements. Optical study shows that TiO₂ possesses direct optical transition with band gap of 3.4 eV.     

Transparent conducting F-doped SnO2 thin films grown by pulsed laser deposition

Transparent conducting fluorine-doped tin oxide (SnO₂:F) films have been deposited on glass substrates by pulsed laser deposition. The structural, electrical and optical properties of the SnO₂:F films have been investigated as a function of F-doping level and substrate deposition temperature. The optimum target composition for high conductivity was found to be 10 wt.% SnF₂ + 90 wt.% SnO₂. Under optimized deposition conditions (T_s = 300 °C, and 7.33 Pa of O₂), electrical resistivity of 5 × 10^− 4 Ω-cm, sheet resistance of 12.5 Ω/□, average optical transmittance of 87% in the visible range, and optical band-gap of 4.25 eV were obtained for 400 nm thick SnO₂:F films. Atomic force microscopy measurements for these SnO₂:F films indicated that their root-mean-square surface roughness ( 6 Å) was superior to that of commercially available chemical vapor deposited SnO₂:F films ( 85 Å).     

Comparison of the electrochemical behavior of CeO2–SnO2 and CeO2–TiO2 electrodes produced by the Pechini method

CeO₂–SnO₂ and CeO₂–TiO₂ thin films were prepared by the Pechini method and their characteristics were compared, using a fractional factorial design to quantify the effect of five preparation variables. It was observed that CeO₂–SnO₂ electrodes show a greater electrochemical response than the CeO₂–TiO₂ films. The best intercalation charge densities were 18.11 and 9.91 mC/cm² for CeO₂–SnO₂ and CeO₂–TiO₂, respectively. Both films were optically inactive with transparencies, in most cases, higher than 90%.     

Structural, electrical and optical characteristics of SnO2:Sb thin films by ultrasonic spray pyrolysis

Antimony-doped tin oxide (SnO₂:Sb) thin films were fabricated by an ultrasonic spray pyrolysis method. The effect of antimony doping on the structural, electrical and optical properties of tin oxide thin films were investigated. Tin(II) chloride dehydrate (SnCl₂·2H₂O) and antimony(III) chloride (SbCl₃) were used as a host and a dopant precursor. X-ray diffraction analysis showed that the non-doped SnO₂ thin film had a preferred (211) orientation, but as the Sb-doping concentration increased, a preferred (200) orientation was observed. Scanning electron microscopy studies indicated that the polyhedron-like grains observed for the non-doped SnO₂ thin films became rounder and decreased in size with the Sb-doping concentration. The lowest resistivity (about 8.4 × 10^− 4 Ω·cm) was obtained for the 3 at.% Sb-doped films. Antimony-doping led to an increase in the carrier concentration and a decrease in Hall mobility. The transmittance level in the near infrared region was lowered with the Sb-doping concentration.     

Hydrogen-radical durability of TiO2 thin films for protecting transparent conducting oxide for Si thin film solar cells

Hydrogen-radical durability of TiO₂ thin films has been investigated under conditions for preparing Si thin film solar cells by catalytic chemical vapor deposition method. It is found that the composition and the optical transmittance of TiO₂ films are almost the same before and after hydrogen-radical exposures with a filament temperature at approximately 1700 °C and a H₂ pressure of approximately 133 Pa. The durability of TiO₂ film has also been observed even under the condition with higher hydrogen-radical density under a filament temperature at approximately 1900 °C, in which SnO₂ and ZnO are easily deoxidized. The application of TiO₂ film as a protecting material of transparent conducting oxide film for Si thin film solar cells are discussed by the hydrogen-radical durability and fundamental properties of TiO₂ thin film.     

二氧化钛/锑掺杂二氧化锡/还原氧化石墨烯复合材料的制备及其光阴极保护性能研究

通过原位生长制备了锑掺杂二氧化锡/还原氧化石墨烯(Sb-SnO₂/RGO)复合材料,再通过水热法生长TiO₂制备了TiO₂/Sb-SnO₂/RGO复合材料。采用X射线衍射、扫描电镜、紫外-可见光、荧光光谱和光电化学等技术对材料的晶体结构、形貌、光吸收特性和电子复合情况进行了表征。结果表明:TiO₂与Sb-SnO₂形成了异质结构,扩大了复合材料的光响应范围,RGO的引入增强了复合材料在可见光区的响应,并提高了电子迁移速率。与TiO₂相比,TiO₂/Sb-SnO₂/RGO复合材料具有更佳的光阴极保护性能。     

WO3/TiO2复合薄膜的制备及其电致变色性能

使用水热法在掺氟SnO₂涂覆的导电玻璃（FTO）基板上生长TiO₂纳米线,随后在TiO₂纳米线上采用水热法生长WO₃纳米线,制备出WO₃/TiO₂复合薄膜。通过循环伏安法（CV）、计时电流法（CA）、计时电量法（CC）等电化学测试技术研究了WO₃/TiO₂复合薄膜的电致变色性能;采用紫外分光光度计对薄膜的着色﹑漂白状态的响应时间进行测试。通过以上测试,计算得到了薄膜的循环稳定性﹑光调制﹑着色效率和切换时间（Y和X）等参数。结果显示WO₃/TiO₂复合薄膜的电致变色性明显提高,其中WO₃/TiO₂复合薄膜可逆性增加了6%,着色效率提高了40.96 cm2/C。      

Synthesis of nanocrystalline photocatalytic TiO2 thin films and particles using sol–gel method modified with nonionic surfactants

A simple sol–gel route has been developed for the preparation of nanocrystalline photocatalytic TiO₂ thin films and particles at 500 °C. The synthesis involved a novel chemistry method employing nonionic surfactant molecules as a pore directing agent along with acetic acid-based sol–gel route without direct addition of water molecules. This study investigated the effect of surfactant type and concentration on the homogeneity, morphology, light absorption, dye adsorption and degradation, and hydrophilicity of TiO₂ films as well as on the structural properties of the corresponding TiO₂ particles. The method resulted in the synthesis of mesoporous TiO₂ material with enhanced structural and catalytic properties including high surface area, large pore volume, pore size controllability, small crystallite size, enhanced crystallinity, and active anatase crystal phase. The prepared TiO₂ thin films were super-hydrophilic and possessed thermally stable spherical bicontinuous mesopore structure with highly interconnected network. Highly porous TiO₂ films prepared with polyethylene glycol sorbitan monooleate surfactant exhibited four times higher photocatalytic activity for the decoloration of methylene blue dye than the nonporous control TiO₂ films prepared without the surfactant. This sol–gel method modified with surfactant templates is useful in the preparation of nanostructured anatase TiO₂ thin films with high photocatalytic activity and desired pore structure.     

Preparation and antibacterial behavior of Fe-doped nanostructured TiO2 thin films

Fe³⁺-doped nanostructured TiO₂ thin films with antibacterial activity were prepared on soda–lime–silica glass slides by using sol–gel technology. Water containing Escherichia coli K-12 with TiO₂ thin films in was exposed to low intensity fluorescent light and antibacterial efficiency was evaluated with spread plate techniques. The films are porous and have anatase phase. Iron ions increased luminous energy utilization as the absorption edge of the Fe³⁺-doped film has a red shift compared to that of the pure TiO₂ film in the UV–VIS absorption spectrum. The bacterial removal efficiency reached 95% at the optimum concentration of iron ion (about 0.5% (mol)) after 120 min irradiation. The antibacterial behavior of the doped TiO₂ films was explicitly observed using scanning electron microscopy and cell wall damage was found.     

Atomic scale faceting and its effect on the grain size distribution of SnO2 thin films during deposition

Abnormal grain growth (AGG) occurs when SnO₂ thin films are deposited by conventional thermal CVD at 475 °C, and high-resolution transmission electron microscopy shows some of the interfaces to be atomically faceted. However, when deposited at 525 °C normal grain growth (NGG) occurs with all the interfaces smoothly curved and atomically rough. This correlation between interface structure and grain growth behavior is consistent with that observed previously in bulk materials. For the application of SnO₂ thin films in sensors and transparent electrodes, 525 °C, which is just above the faceting transition temperature, was found to be the optimum deposition temperature due to its small grain size and high surface to volume ratio.     

Lithographic patterning of benzoylacetone modified SnO2 and SnO2:Sb thin films

The synthesis of directly UV-photopatternable pure and antimony-doped organo-tin materials is presented. UV-photopatternability has been achieved by using the synthesized benzoylacetone modified tin and antimony 2-isopropoxyethoxides. Photopatterned pure and antimony-doped organo-tin films are crystallized by thermal annealing in order to obtain conductive SnO₂ and Sb:SnO₂ thin films. The molar ratio between benzoylacetone and metal alkoxides has to be 2 in order to obtain crack-free, good-quality structures. The effects of UV-irradiation, increasing antimony doping level and benzoylacetone concentration on the electrical properties of the single-layered films are analyzed. The highest obtained conductivity was 20 S/cm. Benzoylacetone concentration and UV-irradiation has only a negligible effect on the film electrical conductivities.     

Electrochromic properties of nanocrystalline MoO3 thin films

Electrochromic MoO₃ thin films were prepared by a sol–gel spin-coating technique. The spin-coated films were initially amorphous; they were calcined, producing nanocrystalline MoO₃ thin films. The effects of annealing temperatures ranging from 100 °C to 500 °C were investigated. The electrochemical and electrochromic properties of the films were measured by cyclic voltammetry and by in-situ optical transmittance techniques in 1 M LiClO₄/propylene carbonate electrolyte. Experimental results showed that the transmittance of MoO₃ thin films heat-treated at 350 °C varied from 80% to 35% at λ = 550 nm (ΔT =  45%) and from 86% to 21% at λ ≥ 700 nm (ΔT =  65%) after coloration. Films heat-treated at 350 °C exhibited the best electrochromic properties in the present study.     

Deposition of Sm2O3 doped CeO2 thin films from Ce(DPM)4 and Sm(DPM)3 (DPM=2,2,6,6-tetramethyl-3,5-heptanedionato) by aerosol-assisted metal–organic chemical vapor deposition

Samarium-doped ceria (SDC) thin films were prepared from Sm(DPM)₃ (DPM = 2,2,6,6-tetramethyl-3,5-heptanedionato) and Ce(DPM)₄ using the aerosol-assisted metal–organic chemical vapor deposition method. -Al₂O₃ and NiO-YSZ (YSZ = Y₂O₃-stabilized ZrO₂) disks were chosen as substrates in order to investigate the difference in the growth process on the two substrates. Single cubic structure could be obtained on either -Al₂O₃ or NiO-YSZ substrates at deposition temperatures above 450 °C; the similar structure between YSZ and SDC results in matching growth compared with the deposition on -Al₂O₃ substrate. A typical columnar structure could be obtained at 650 °C on -Al₂O₃ substrate and a more uniform surface was produced on NiO-YSZ substrate at 500 °C. The composition of SDC film deposited at 450 °C is close to that of precursor solution (Sm : Ce = 1 : 4), higher or lower deposition temperature will both lead to sharp deviation from this elemental ratio. The different thermal properties of Sm(DPM)₃ and Ce(DPM)₄ may be the key reason for the variation in composition with the increase of deposition temperature.     

SiO2/TiO2 thin films with variable refractive index prepared by ion beam induced and plasma enhanced chemical vapor deposition

SiO₂/TiO₂ optical thin films with variable compositions have been prepared by ion beam induced and plasma enhanced chemical vapour deposition (IBICVD and PECVD). While the films obtained by IBICVD were very compact, the PECVD ones with a high content of Ti presented a columnar microstructure. The formation of Si–O–Ti bonds and a change in the environment around titanium from four- to six-coordinated has been proved by vibrational and X-ray absorption spectroscopies. The refractive index increased with the titanium content from 1.45 to 2.46 or 2.09 for, respectively, the IBICVD and PECVD films. Meanwhile, the band gap decreased, first sharply and then more smoothly up to the value of pure TiO₂. It is concluded that the optical properties of SiO₂/TiO₂ thin films can be properly tailored by using these two procedures.     

Ag-Ag2O/TiO2-g-C3N4纳米复合材料的制备及可见光催化性能

近年来,半导体光催化技术作为一项快速发展的新型环保技术,在降解水体中污染物和可再生清洁能源的生产领域有很大的应用前景。本文以所制备出的20 wt%类石墨烯碳氮化合物(g-C₃N₄)/TiO₂为基质,利用水热法中纳米Ag颗粒部分氧化行为成功合成了Ag修饰异质结型Ag-Ag₂O/TiO₂-g-C₃N₄复合材料。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)、紫外-可见漫反射光谱(UV-Vis DRS)、光致荧光光谱(PL)、瞬态光电流响应等分析测试手段对Ag-Ag₂O/TiO₂-g-C₃N₄复合材料的晶体结构、形貌、光学性质等进行表征和分析。以亚甲基蓝溶液为目标降解物,研究了Ag-Ag₂O/TiO₂-g-C₃N₄复合材料的可见光催化性能。结果表明:在纳米Ag颗粒修饰的Ag-Ag₂O/TiO₂-g-C₃N₄复合材料中,Ag部分氧化成Ag₂O;与g-C₃N₄的协同作用使Ag-Ag₂O/TiO₂-g-C₃N₄复合催化剂具有良好的可见光催化活性;可见光照射4 h后,Ag-Ag₂O/TiO₂-g-C₃N₄复合催化剂对亚甲基蓝的降解率接近50%。      

SnO2:Ga thin films as oxygen gas sensor

Ga-doped SnO₂ thin films deposited by spray pyrolysis were investigated as oxygen gas sensors. Gallium was added to the films to enhance the catalytic activity of the surface’s film to oxygen. Film resistance was studied in an environment of dry air loaded with oxygen in excess at partial pressures in the range from 0 to 8.78×10³ Pa. The best sensitivity lies close to partial pressures of 133.3 Pa. Film sensitivity reach a maximum at 350 °C. For this temperature and a doping concentration of 3 at.% of Ga in the starting solution, a sensitivity up to 2.1 was obtained.     

Structure and electrical properties of (100)-oriented Pb(Zn1/3Nb2/3)O3–Pb(Mg1/3Nb2/3)O3–PbTiO3 thin films on La0.7Sr0.3MnO3 electrode by chemical solution deposition

(100)-oriented 0.462Pb(Zn_1/3Nb_2/3)O₃–0.308Pb(Mg_1/3Nb_2/3)O₃–0.23PbTiO₃ (PZN-PMN-PT) perovskite ferroelectric thin films were prepared on La_0.7Sr_0.3MnO₃/LaAlO₃ (LSMO/LAO) substrate via a chemical solution deposition route. The perovskite LSMO electrode was found to effectively suppress the pyrochlore phase while promote the growth of the perovskite phase in the PZN-PMN-PT film. The film annealed at 700 °C exhibited a high dielectric constant of 2130 at 1 kHz, a remnant polarization, 2P_r, of 29.8 μC/cm², and a low leakage current density of 7.2 × 10^− 7 A/cm² at an applied field of 200 kV/cm. The ferroelectric polarization was fatigue-free at least up to 10¹⁰ cycles. Piezoelectric coefficient, d₃₃, of 48 pm/V was also demonstrated. The results showed that much superior properties could be achieved with the PZN-PMN-PT thin films on the solution derived LSMO electrode than on Pt electrode by sputtering.     

玻璃固载TiO2/纳米纤维素复合薄膜的制备及其光催化性能

将微晶纤维素溶解于NaOH-尿素的低温溶液中形成纤维素溶液, 在水浴中再生形成纳米纤维素溶液。然后将纳米纤维素溶液与TiO₂(P25)混合, 并添加少量的钛酸正丁酯作为交联剂形成复合溶液。将制备得到的复合溶液通过流延法固载到玻璃片表面形成玻璃固载的TiO₂/纳米纤维素复合膜。通过SEM、XRD表征了复合膜的形貌与结构。将玻璃固载的TiO₂/纳米纤维素复合膜在紫外光下进行光催化降解甲基橙(MO)以评估复合膜的光催化性能, 研究了纳米TiO₂含量对复合膜光催化性能的影响, 复合膜的重复使用性能以及光降解的动力学过程。结果表明: 复合膜对MO的光催化降解能力可达90%以上, 与纯TiO₂粉末相当, 并重复使用3次光催化性能基本保持不变。复合膜对甲基橙的降解动力学符合一级动力学特征。当纳米TiO₂相对于纤维素的质量分数为33.3%时, 光催化活性最高, 动力学速率常数为0.035 min^-1。     

Influence of the common varistor dopants (CoO, Cr2O3 and Nb2O5) on the structural properties of SnO2 ceramics

The influence of dopants commonly used in SnO₂ varistor ceramics, such as CoO, Cr₂O₃ or Nb₂O₅, on the structural properties of SnO₂ was investigated. Several SnO₂-based ceramics containing only one of the dopants were prepared and characterized. Spectroscopic investigations [visible, near infrared (IR) and IR region] were performed to obtain information about dopants valence states inside the ceramics, as well as about their influence on electronic structure of the material. Structural properties were investigated by X-ray diffraction analysis and mechanisms of dopant incorporation were proposed. Obtained results were confirmed with results of the electrical measurements. Microstructural changes in doped ceramics were investigated by scanning electron microscopy (SEM) analysis that showed great differences in densities, grain size, and morphology of the SnO₂ ceramics depending on type of dopants and their distribution.     

Enhanced ferroelectric properties of multilayer SrBi2Ta2O9/SrBi2Nb2O9 thin films for NVRAM applications

Ferroelectric SrBi₂Ta₂O₉/SrBi₂Nb₂O₉ (SBT/SBN) multilayer thin films with various stacking periodicity were deposited on Pt/TiO₂/SiO₂/Si substrate by pulsed laser deposition technique. The X-ray diffraction patterns indicated that the perovskite phase was fully formed with polycrystalline structure in all the films. The Raman spectra showed the frequency of the O–Ta–O stretching mode for multilayer and single layer SrBi₂(Ta_0.5Nb_0.5)₂O₉ (SBNT) samples was 827–829 cm⁻¹, which was in between the stretching mode frequency in SBT (813 cm⁻¹) and SBN (834 cm⁻¹) thin films. The dielectric constant was increased from 300 (SBT) to 373 at 100 kHz in the double layer SBT/SBN sample with thickness of each layer being 200 nm. The remanent polarization (2P_r) for this film was obtained 41.7 μC/cm², which is much higher, compared to pure SBT film (19.2 μC/cm²). The coercive field of this double layer film (67 kV/cm) was found to be lower than SBN film (98 kV/cm).