Improvement of the morphological and electrical characteristics of Al3+, Fe3+ and Bi3+-doped TiO2 compact thin films and their incorporation into hybrid solar cells

Compact titanium dioxide (TiO₂) hole-blocking layers are commonly employed in organic-inorganic solar cells, however, their importance in terms of morphology and electrical conductivity is frequently overlooked in this novel type of solar energy converters. In this work, single TiO₂ thin films were prepared by a sol-gel method, observing large pinhole densities and low electrical conductivities. As a means to solve the morphological issue, the deposition of a second TiO₂ film was explored, which effectively reduced the surface irregularities obtained in single oxide films. The limited electrical conductivity of single and double layers was successfully increased by doping with the trivalent cations of aluminum, iron (III) and bismuth (III), observing an increase from 2.48 × 10⁻⁸ S/cm for an undoped TiO₂ double layer to 51.41 × 10⁻⁸ S/cm for a Fe³⁺-doped TiO₂ double layer. The incorporation of these hole blocking layers in hybrid solar cells led to further insights in the important role of trivalent doping cations in the transference and transport of electrons on the surface and in the bulk of the prepared TiO₂ compact films.     

Hybrid electrochromic film based on polyaniline and TiO2 nanorods array

Titanium dioxide (TiO₂) nanorods (NRs) array was successfully prepared via hydrothermal method on fluorine doped tinoxide (FTO) coated transparent conductive glass substrate. The hybrid film of polyaniline (PANI)/TiO₂ NRs was achieved through electrochemical polymerization of aniline onto the TiO₂ NRs array film. The electrochromic and optical properties of the hybrid film were investigated by cyclic voltammetry (CV), amperometric i–t and UV–vis spectroscopy. The results indicate that the hybrid film has long term stability and reversible color changes after cyclic voltammetry scans for 200 circles. The PANI/TiO₂ NRs hybrid film can show three different colors. Response time of PANI/TiO₂ NRs hybrid film is about 0.7 s and 2.6 s at different states, respectively. The TiO₂ NRs array and the loose, porous surface among the hybrid film facilitate charge transmission and also provide large surface area for electrochemical reaction.     

Capacitance-voltage analysis of a high-k dielectric on silicon

Device characteristics of TiO₂ gate dielectrics deposited by a sol-gel method and DC sputtering method on a P-type silicon wafer are reported. Metal-oxide-semiconductor capacitors with Al as the top electrode were fabricated to study the electrical properties of TiO₂ films. The films were physically characterized by using X-ray diffraction, a capacitor voltage measurement, scanning electron microscopy, and by spectroscopy ellipsometry. The XRD and DST-TG indicate the presence of an anatase TiO₂ phase in the film. Films deposited at higher temperatures showed better crystallinity. The dielectric constant calculated using the capacitance voltage measurement was found to be 18 and 73 for sputtering and sol-gel samples respectively. The refractive indices of the films were found to be 2.16 for sputtering and 2.42 for sol-gel samples.     

Effect of titanium dioxide (TiO2) seed layer on the phase composition of 0.7Pb (Mg1/3Nb2/3)O3-0.3PbTiO3 film prepared by pulsed laser deposition

Lead-magnesium niobate-lead titanate (PMN-PT) thin films with and without the TiO₂ seed layer were deposited on Pt/Ti/SiO₂/Si substrates through pulsed laser deposition. The study aimed to characterize the effect of the TiO₂ seed layer on the phase composition and properties of PMN-PT film. Without the TiO₂ seed layer, the pure perovskite phase could be obtained in the thinner PMN-PT film while with the TiO₂ seed layer, the pure perovskite phase was formed in the thicker PMN-PT film. The ferroelectric properties of PMN-PT films with the TiO₂ seed layer were exhibited. As a result, the maximum amount of remnant polarization reached the amount of 32 μC/cm² for the PMN-PT thin film with the TiO₂ seed layer.     

Room‐Temperature Synthesis of Porous Nanoparticulate TiO2 Films for Flexible Dye‐Sensitized Solar Cells

A novel room‐temperature method for the preparation of porous TiO₂ films with high performance in dye‐sensitized solar cells (DSSCs) has been developed. In this method a small amount of Ti^IV tetraisopropoxide (TTIP) is added to an ethanolic paste of TiO₂ nanoparticles, where it hydrolyzes in situ and connects the TiO₂ particles to form a homogenous and mechanically stable film of up to 10 μm thickness without crack formation. Residual organics originating from the TTIP were removed by UV–ozone treatment of the films, leading to a remarkable improvement of the cell efficiency. Intensity‐modulated photocurrent/voltage spectroscopy (IMPS/IMVS) showed that the main effect of the UV–ozone treatment is to suppress the recombination of photogenerated electrons, thereby extending their lifetime. The efficiency was further increased by preheating the TiO₂ nanoparticles before the paste preparation to remove contaminants originating from the preparation process of the particles. Solar‐to‐electric energy conversion efficiencies of 4.00 and 3.27 % have been achieved for cells with conductive glass and plastic film substrates, respectively, under illumination with AM 1.5 (100 mW cm^–2) simulated sunlight.     

Inorganic Macroporous Films from Preformed Nanoparticles and Membrane Templates: Synthesis and Investigation of Photocatalytic and Photoelectrochemical Properties

Colloidal dispersions of titania, zirconia, tin oxide, indium oxide, and ceria have been successfully used to impregnate membrane templates and form the respective metal oxide (MO) porous films. The use of alumina and iron oxide sols in the same procedure, however, resulted in compact structures. By mixing different nanoparticle solutions before impregnation, final inorganic films containing two metal oxides, of variable metal oxide ratios, were obtained. The porous inorganic materials were analyzed in terms of surface area, pore size, film thickness, and crystallinity. The mechanism of nanoparticle infiltration and particle adsorption to the template walls is proposed based on the stability of the inorganic film and a study of the influence of either the sol concentration or washing times on the amount of inorganic substance incorporated in the hybrid material. The photocatalytic decomposition of an organic pollutant, 2‐chlorophenol, was demonstrated for the porous titania material along with the structures containing mixtures of titania with zirconia, indium oxide, and tin oxide. A ratio of 9:1 TiO₂/MO gave the highest photocatalytic activity, which was higher than the activity of Degussa P25 for the TiO₂/In₂O₃ and TiO₂/SnO₂ systems under the same conditions. The titania films have also been attached to substrates—glass or indium tin oxide (ITO) surfaces—and the photoelectrochemical properties of the porous film attained. A comparison with a spin‐coated titania film (prepared from the same colloidal dispersion) showed that the structured porous inorganic film has two times the photoelectrochemical efficiency as the spin‐coated film.     

Analysis of the stress and interfacial reactions in Pt/Ti/SiO2/Si for use with ferroelectric thin films

The microstructure of the Pt/Ti/SiO₂/Si structure has been investigated by scanning and transmission electron microscopy. Pt films of 100 nm thickness deposited by sputtering or evaporation onto unheated substrates gave complete coverage of the underlying Ti layer and showed a granular and faceted structure with grains ∼20 nm in diameter. They did not exhibit hillocks or surface TiO_x formation. X-ray diffraction was used to examine the film stress through use of the sin²ψ method with bulk values for the elastic constants (v=0.39, E=162 GPa). The as-deposited sputtered film had a compressive stress of ∼540 MPa, while the evaporated films had tensile stresses of ∼630 MPa. The films then received a 400°C rapid thermal anneal (RTA) for 90 s and a subsequent RTA of 650°C for 30s. Further investigation of the film stresses and microstructure were made after each annealing step. After the low temperature anneal, the film stress for the sputtered film became tensile. Plan-view sections examined by transmission electron microscopy (TEM) showed that the as-deposited sputtered films were dense but became porous after annealing. Initially, the evaporated films had a less dense microstructure, but were more stable with annealing. Little change in the stress for the evaporated film was observed after this initial low temperature annealing step. Additional annealing of the evaporated and sputtered samples caused complete consumption of the Ti layer including some TiO_x formation from the underlying SiO₂ layer and marked interaction with the Pt; however, little change in the stress was found. The surface of the Pt film revealed larger grains, but otherwise remained unaffected. The underlying phase changes were minimized once the Ti layer had reacted with the Pt. Due to the ratio of the layers, Pt:Ti of 2:1, the surface of the Pt was unaffected.     

Al/N共掺杂TiO2薄膜的制备及光学性能

采用溶胶-凝胶旋涂法(Sol-Gel Spin-Coating Method)制备了Al掺杂量为3.00at%,N掺杂量分别为6.00at%,7.00at%,8.00at%和9.00at%的Al/N共掺杂TiO₂薄膜样品。对样品测试的结果表明,共掺杂样品依旧保留了TiO₂的基本结构,并且Al/N共掺杂样品的晶粒尺寸有不同程度的减小,使样品表面得以修饰,变得更加均匀、平整。共掺杂样品吸收边都出现了不同程度的红移,在紫外光区以及可见光区的吸光性都有所增强。N掺杂量为7.00at%时,(101)衍射峰值最大,峰型最尖锐,所得到的TiO₂薄膜的光学性能最好。共掺杂后的样品与本征TiO₂相比带隙值都有所减小,且最小值为2.873eV。以上结果表明Al/N共掺杂TiO₂薄膜使其光学性能得到了改善。     

Al2O3/TiO2 nanolaminate gate dielectric films with enhanced electrical performances for organic field-effect transistors

Nanolamination has entered the spotlight as a novel process for fabricating highly dense nanoscale inorganic alloy films. OFET commercialization requires, above all, excellent dielectric properties of gate dielectric layer. Here, we describe the fabrication and characterization of Al–O–Ti (AT) nanolaminate gate dielectric films using a PEALD process, and their OFET applications. The AT films exhibited a very smooth surface (R_q < 0.3 nm), a high dielectric constant (17.8), and a low leakage current (8.6 × 10⁻⁹ A/cm² at 2 MV/cm) compared to single Al₂O₃ or TiO₂ films. Importantly, a 50 nm thick AT film dramatically enhanced the value of μFET (0.96 cm²/V) on a pentacene device, and the high off-current level in a single TiO₂ film was effectively reduced. The nanolamination process removes the drawbacks inherent in each single layer so that the AT film provides excellent dielectric properties suitable for fabricating high-performance OFETs. Triethylsilylethynyl anthradithiophene (TES-ADT), a solution-processable semiconductor, was combined with the AT film in an OFET, and the electrical properties of the device were characterized. The excellent dielectric properties of the AT film render nanolamination a powerful strategy for practical OFET applications.     

Sono‐ and Photochemical Routes for the Formation of Highly Dispersed Gold Nanoclusters in Mesoporous Titania Films

A sono‐ and photochemical approach has been developed to incorporate highly dispersed gold nanoclusters into mesoporous TiO₂ films. The first step involves the sonication of a TiO₂ film immersed in a gold chloride solution. This effectively removes the air trapped in the porous film matrix and drives the gold chloride into the pore channels, leading to a homogeneous adsorption of ionic Au in the TiO₂ mesoporous matrix. The second step takes advantage of the photocatalytic property of TiO₂ to reduce the adsorbed Au ions to Au⁰. As the gold nanoclusters thus produced are stabilized by the TiO₂ mesonetwork, no organic capping molecules are required. Highly dispersed Au/TiO₂ nanoheterojunction arrays can be obtained using this interesting approach.     

Performance analysis of dye solar cell with additional TiO2 layer under different light Intensities

Deployment of dye solar cells (DSCs) for building integration application would require a highly efficient solar cell that work well in diffused light. In order to improve the efficiency of dye solar cell, an additional layer of ultrathin anatase titanium dioxide (TiO₂) has been deposited for strengthening the adhesion of the porous TiO₂-based photo electrode to the conductive transparent substrate, which can lead to an enhancement in electron transportation. Fabricated cells of 1 cm² area were tested under different light intensities (100, 33 and 10 mW cm⁻²) and characterized by scanning electron microscopy (SEM), Raman spectroscopy and electrochemical impedance spectroscopy (EIS). Analysis showed an increment in overall quantum conversion efficiency (η), as high as 35% compared to the standard cell without the additional layer of TiO₂. EIS analysis has proven that the additional ultrathin anatase layer has improved the collection efficiency (Φ_COLL) as the result of the enhancement in both electron transport and lifetime within the porous TiO₂ film which translated into better conversion efficiency of DSCs.     

Low-cost TiO2/Sb2(S,Se)3 heterojunction thin film solar cell fabricated by sol-gel and chemical bath deposition

Low cost TiO₂/ Sb₂(S, Se)₃ heterojunction thin film solar cell are prepared successfully by using sol-gel and chemical bath deposition. At first, TiO₂ thin film is prepared on the ITO-coated glass substrate by a simple sol-gel and dip-coating method. Subsequently, Sb₂(S, Se)₃ film is fabricated on TiO₂ by selenizing the Sb₂S₃ film prepared by chemical bath deposition (CBD). The heat-treated process of TiO₂ and Sb₂(S, Se)₃ films has been discussed, respectively. After being heat-treated at 550 °C for TiO₂ and 290 °C for Sb₂(S, Se)₃ films, the photovoltaic devices are completed with the conductive graphite as electrode. The J-V characteristics of TiO₂/ Sb₂(S, Se)₃ solar cell are measured and the open circuit voltage (V_oc) of this cell is about 350 mV.     

ZnO-Coated TiO2 Nanotube Arrays for a Photoelectrode in Dye-Sensitized Solar Cells

In dye-sensitized solar cells, highly ordered TiO₂ nanotube arrays as a photoelectrode have higher charge collection efficiencies than a nanoparticle-based structure due to their faster charge percolation and slower recombination of electrons. Highly ordered TiO₂ nanotube arrays were grown by anodic oxidation of 0.5-mm-thick titanium foil. To increase the conversion efficiency of dye-sensitized solar cells with TiO₂ nanotube arrays, the surface of the TiO₂ nanotube arrays was modified by zinc oxide thin films. The ZnO thin film was formed by atomic layer deposition. The thin film was conformal on the inner and outer walls of TiO₂ nanotube arrays. ZnO thin film improved the short circuit current (J _sc) and open circuit voltage (V _oc) due to increasing specific surface area from particulates of ZnO thin film and increasing the surface charge induced from the isoelectric point. The power conversion efficiency of dye-sensitized solar cells with ZnO thin film on 4.5-μm-thick TiO₂ nanotube arrays was 1.43%. Microstructure and phase were observed by scanning electron microscopy, x-ray diffractometry, and transmission electron microscopy.     

Femtosecond laser deposition of TiO2 nanoparticle-assembled films with embedded CdS nanoparticles

Based on the normal pulsed laser ablation method,femtosecond pulsed laser deposition（fs-PLD）is adopted in vacuum for the production of TiO2nanoparticle-assembled films.We study the morphology and electronic characteristics of TiO2nanoparticle-assembled films deposited at different oxygen background gas pressures from high vacuum（~10-4Pa）to 100 Pa and different deposition time.Our results show that TiO2nanoparticle-assembled films obtained in high vacuum present both a mixture with rutile phase and anatase phase and a pure rutile phase.At the same time,there are more mesoporous structures in the film after annealing,which is beneficial for the enhancement of photocatalytic activity.In water splitting experiment,part of the TiO2nanoparticle-assembled films embedded with a small mass fraction of CdS nanoparticles（~5%）present an interesting photocurrent enhancement with a maximum value of~0.2mA/cm2under a solar simulator.     

C-V characteristics of metal-titanium dioxide-silicon capacitors

Titanium dioxide capacitors were fabricated on silicon wafers using electron-beam evaporation. The TiO₂ films varied in thickness from 500 to 2000 Å. Post-deposition oxidation at 1000°C in dry O₂ was used to promote stoichiometric conversion of the films to the rutile phase. Capacitive densities of greater than 2 pf/sq. mil were obtained (dielectric constants ranged from 4 to 40). For long oxidation times, significant silicon dioxide grows under the TiO₂ as a result of oxygen diffusing through the TiO₂ film. Titanium was also shown to diffuse into the silicon during the oxidation cycle resulting in an n-type diffusion. Surface state densities ranging from 10¹¹ to 5 × 10¹¹ cm^?2 eV^?1 at midgap were obtained for good devices. Longer oxidation times result in lower capacitance, leakage current and surface state density.     

Silicon and aluminum co-doping of titania nanoparticles: Effect on thermal stability,particle size and photocatalytic activity

Silicon and aluminum co-doped titania (TiO₂) nanoparticles were fabricated by the sol–gel method. To investigate the effects of silicon and aluminum co-doping on thermal stability, microstructure and photocatalytic activity of TiO₂ nanoparticles. Six batches of silicon-aluminum doped samples were characterized by X-ray diffraction (XRD), BET surface area measurement, scanning electron microscopy (SEM) and UV–vis absorption spectra. The photocatalytic activities were evaluated by the degradation of methylene blue (MB) under UV light irradiation. Experimental results revealed that silicon and aluminum co-doping helped to improve the crystal phase transition temperature of titania to 1200 °C and also decrease the particle size at high calcination temperature. A significant blue-shift was observed in the spectrum of UV–vis absorption. Additionally, it was found that silicon and aluminum co-doping exhibited better photocatalytic activity. The formation defects from solid solution reaction between Si⁴⁺, Al³⁺ and TiO₂ effectively inhibits the crystal phase transition and grain growth of TiO₂ nanoparticles.     

Formation of Oxynitride as the Photocatalytic Enhancing Site in Nitrogen‐Doped Titania Nanocatalysts: Comparison to a Commercial Nanopowder

A nitrogen‐doped TiO₂ nanocolloid has been successfully prepared and its properties compared with the commercially available TiO₂ nanomaterial, Degussa P25. Several characterization techniques, X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), transmission electron spectroscopy (TEM), Fourier transform infrared (FT‐IR) spectroscopy, Raman scattering, and UV‐visible reflectance spectra, are combined in order to determine the crystal phase and grain size, shape, degree of nitrogen incorporation, and nature of the resultant oxynitride chemical bonding on the surface and in the bulk. The high relative photocatalytic activity of the nitrogen doped‐TiO₂ nanocolloid is evaluated through a study of the decomposition of methylene blue under visible light excitation. The ease and degree of substitutional‐insertional nitrogen doping is held accountable for the significant increase in photocatalytic activity in the porous nanocolloid versus the nitrided commercial nanopowder. It is suggested that the nitrogen incorporation produces an NO bonding region as evidenced by the resulting XPS spectrum.     

Syntheses,Li Insertion,and Photoactivity of Mesoporous Crystalline TiO2

Ordered mesoporous rutile and anatase TiO₂ samples are prepared using mesoporous silica SBA‐15 as template and freshly synthesized titanium nitrate and titanium chloride solutions as precursors. The rutile material formed from the nitrate solution is monocrystalline and contains minimal amounts of Si with a Si:Ti ratio of 0.031(4), whereas the anatase material formed from the chloride solution comprises nanocrystals and contains a higher content of Si with a Si:Ti ratio of 0.18(3). It is found that control of temperature and selection of Ti‐containing precursor play important roles in determining the crystal phase and crystallinity. A possible formation mechanism of porous crystalline TiO₂ is suggested. Characterization of these porous materials is performed by XRD, HRTEM, and nitrogen adsorption/desorption. SBA‐15‐templated mesoporous rutile TiO₂ exhibits a higher Li ion insertion capability than KIT‐6‐templated TiO₂ due to its larger surface area. Likewise mesoporous anatase TiO₂:SiO₂ composite has a better photoactivity than bulk TiO₂ or TiO₂‐loaded SBA‐15 for bleaching methylene blue.     

Spray-Dried TiO2(B)-Containing Photocatalytic Glass-Ceramic Nanobeads

Glass-ceramic nanospheres of molar composition 0.83 SiO₂ · 0.17 TiO₂ are produced by the sol-gel spray-drying method followed by controlled heat treatments up to 1200 ° C. TiO₂(B) and anatase nanocrystals are precipitated in the glassy matrix: the latter phase gradually predominates with increasing ceramization temperature and time, in parallel to an overall increase in crystal sizes. The nanospheres exhibit evident photocatalytic activity under UV-A irradiation, especially at annealing stages involving a comparatively higher amount of TiO₂(B) and smaller crystals. The occurrence of TiO₂(B) in this simplified binary glass-ceramic material underlines the key role of this phase in the dynamics of crystallizing TiO₂-bearing silicate melts.     

Influence of Ti film thickness and oxidation temperature on TiO2 thin film formation via thermal oxidation of sputtered Ti film

Single-phase rutile TiO₂ films with good crystallinity were obtained by thermal oxidation of sputtered Ti films on Si and quartz substrates. The influence of the Ti film thickness on oxidation was systematically investigated. A temperature of 823 K was sufficient to fully oxidize Ti films of <0.2 μm in thickness, but 923 K was required for complete oxidation of thicker films. The crystal structure, phase, composition, and optical properties of the TiO₂ films were investigated using X-ray diffraction (XRD), Raman spectroscopy, energy-dispersive X-ray analysis (EDAX), and UV-vis-NIR spectroscopy. XRD and Raman analyses showed that the TiO₂ films are rutile phase. The bandgap of the TiO₂ films decreased with increasing thickness. A growth mechanism for TiO₂ thin films due to thermal oxidation of sputtered Ti films is proposed. Oxidation commences from the surface and proceeds inside the bulk and Ti→TiO₂ phase transformation occurs via different intermediate phases. We found that the oxidation temperature rather than the duration is the dominant factor in the growth of TiO₂ thin films.