A study on the electron transport properties of TiO2 electrodes in dye-sensitized solar cells

The influences of annealing temperature and different poly (ethylene glycol) (PEG) contents in nano-crystalline TiO₂ electrodes with and without N3 dye on the electron transfer in a dye-sensitized solar cell (DSSC) were investigated. It is found that the power conversion efficiency increases with the increase in annealing temperature and becomes saturated at 400–500 °C, and further increase lowers the performance which is consistent with the enhancement of the crystalline TiO₂ particles observed in X-ray diffraction (XRD) patterns and scanning electron microscopy (SEM) images. Electrochemical impedance spectroscopy (EIS) also confirms this behavior. These results have been further verified by studying the electron lifetimes (τ_e) and electron diffusion coefficients (D_e) of a bare TiO₂ and a dye-sensitized TiO₂ film using a pulsed laser spectrometer. It is noted that both the electron lifetime and the electron diffusion coefficient increase with the increase in annealing temperature. However, the evolution of rutile TiO₂ begins beyond 600 °C and this lowers the dye absorbance and the electron diffusion coefficients of TiO₂ electrodes. A similar study was made by varying the content of the PEG in the TiO₂ films. It is found that with the increase in the PEG content, a decrease in the electron lifetimes and a little hike in the electron diffusion coefficients are noted, where the cell performance remains almost the same. In addition, the dye adsorption decreases the electron lifetime and increases the electron diffusion coefficient of the TiO₂ films regardless of the PEG content and the annealing temperature.     

Direct Z-scheme anatase/rutile bi-phase nanocomposite TiO2 nanofiber photocatalyst with enhanced photocatalytic H2-production activity

Design and preparation of direct Z-scheme anatase/rutile TiO₂ nanofiber photocatalyst to enhance photocatalytic H₂-production activity via water splitting is of great importance from both theoretical and practical viewpoints. Herein, we develop a facile method for preparing anatase and rutile bi-phase TiO₂ nanofibers with changing rutile content via a slow and rapid cooling of calcined electrospun TiO₂ nanofibers. The phase structure and composition, surface morphology, specific surface area, surface chemical composition and element chemical states of TiO₂ nanofibers were analyzed by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), nitrogen adsorption and X-ray photoelectron spectroscopy (XPS). By a rapid cooling of 500 °C-calcined electrospun TiO₂ precursor, anatase/rutile bi-phase TiO₂ nanofibers with a roughly equal weight ratio of 55 wt.% anatase and 45 wt.% rutile were prepared. The enhanced H₂ production performance was observed in the above obtained anatase/rutile composite TiO₂ nanofibers. A Z-scheme photocatalytic mechanism is first proposed to explain the enhanced photocatalytic H₂-production activity of anatase/rutile bi-phase TiO₂ nanofibers, which is different from the traditional heterojunction electron–hole separation mechanism. This report highlights the importance of phase structure and composition on optimizing photocatalytic activity of TiO₂-based material.     

Oxidative photoelectrochemical technology with Ti/TiO2 anodes

Rutile and anatase TiO₂ films have been grown on Ti plates by thermal (500–800°C) and anodic oxidation followed by thermal annealing (400–500°C), respectively. The photoelectrochemical efficiency of these photoanodes, evaluated by current density measurements in the photooxidation of 4-methoxybenzyl alcohol in deaerated CH₃CN, has been determined. The photocurrent efficiency increases with the thickness of the TiO₂ rutile film up to 1 μm (the most efficient thickness). At the wavelengths furnished by the irradiation apparatus similar thicknesses of anatase and rutile films show nearly the same efficiencies. Anodic bias produces similar relative increases of current intensity in both crystalline forms.     

The influence of surface morphology of TiO2 coating on the performance of dye-sensitized solar cells

The optimization of solar energy conversion efficiency of dye-sensitized solar cells (DSSCs) was investigated by the tuning of TiO₂ photoelectrode's surface morphology. Double-layered TiO₂ photoelectrodes with four different structures were designed by the coating of TiO₂ suspension, incorporated with low and high molecular weight poly(ethylene glycol) as a binder. Among these four systems, P2P1, where P1 and P2 correspond to the molecular weight of 20,000 and 200,000, respectively, showed the highest efficiency under the conditions of identical film thickness and constant irradiation. This can be explained by the larger pore size and higher surface area of P2P1 TiO₂ electrode than the other materials as revealed by scanning electron microscopic (SEM) and Brunauer–Emmett–Teller (BET) analyses. Electrochemical Impedance Spectroscopy (EIS) analysis shows that P2P1 formulation displayed a smaller resistance than the others at the TiO₂/electrolyte interface. The best efficiency (η) of 9.04% with the short-circuit photocurrent density (J_sc) and open-circuit voltage (V_oc) of 18.9 mA/cm² and 0.74 V, respectively, was obtained for a solar cell by introducing the light-scattering particles to the TiO₂ nanoparticles matrix coated on FTO electrode having the sheet resistivity of 8 Ω/sq.     

Low-temperature synthesis of TiO2 nanoparticles and preparation of TiO2 thin films by spray deposition

Low-temperature (180–240 °C) synthesis of nanocrystalline titanium dioxide (TiO₂) by surfactant-free solvothermal route is investigated. Titanium iso-propoxide is used as the precursor and toluene as the solvent. Different precursors to solvent weight ratios have been used for the synthesis of TiO₂ nanoparticles. For the weight ratios 15/100, 25/100 and 35/100 the X-ray diffractograms show the formation of nanocrystalline TiO₂. The X-ray diffraction and transmission electron microscopy studies shows that the product has anatase crystal structure (for temperatures <200 °C) with average particle size below 15 nm. The films deposited by spray deposition method using these nanoparticles show the crystalline and porous nature of the films. The present method of deposition also avoids the post-treatment (sintering) of the films. The nanoparticles thus prepared and the films can be used for gas sensing and biological applications and also as photo-electrodes for dye-sensitized solar cells.     

Preferential oxidation of CO in H2 stream on Au/CeO2–TiO2 catalysts

A series of Au catalysts supported on CeO₂–TiO₂ with various CeO₂ contents were prepared. CeO₂–TiO₂ was prepared by incipient-wetness impregnation with aqueous solution of Ce(NO₃)₃ on TiO₂. Gold catalysts were prepared by deposition–precipitation method at pH 7 and 65 °C. The catalysts were characterized by XRD, TEM and XPS. The preferential oxidation of CO in hydrogen stream was carried out in a fixed bed reactor. The catalyst mainly had metallic gold species and small amount of oxidic Au species. The average gold particle size was 2.5 nm. Adding suitable amount of CeO₂ on Au/TiO₂ catalyst could enhance CO oxidation and suppress H₂ oxidation at high reaction temperature (>50 °C). Additives such as La₂O₃, Co₃O₄ and CuO were added to Au/CeO₂–TiO₂ catalyst and tested for the preferential oxidation of CO in hydrogen stream. The addition of CuO on Au/CeO₂–TiO₂ catalyst increased the CO conversion and CO selectivity effectively. Au/CuO–CeO₂–TiO₂ with molar ratio of Cu:Ce:Ti = 0.5:1:9 demonstrated very high CO conversion when the temperature was higher than 65 °C and the CO selectivity also improved substantially. Thus the additive CuO along with the promoter and amorphous oxide ceria and titania not only enhances the electronic interaction, but also stabilizes the nanosize gold particles and thereby enhancing the catalytic activity for PROX reaction to a greater extent.     

Antireflecting–passivating dielectric films on crystalline silicon solar cells for space applications

Antireflecting–passivating TiO₂–SiO₂ double layers on crystalline silicon (Si) were optimized and characterized for space solar cells applications. In the numeric optimization, the MgF₂–glass–adhesive–TiO₂–SiO₂–Si structure was considered. In order to fabricate the TiO₂–SiO₂ double layer, titanium films were deposited on Si wafers in a vacuum chamber, and then, the sample was annealed in oxygen at high temperatures. Glasses with evaporated MgF₂ thin films were bonded to the TiO₂–SiO₂–Si samples so as to obtain the complete structure. A gain of up to 23.5% in the maximum power is demonstrated for simulated c-Si solar cells using the optimized structure. Characterization of the TiO₂–SiO₂–Si structure using transmission electron microscopy (TEM) and X-ray reflectivity (XRR) as well as optical characterization are presented.     

Investigation on the electron transfer between anatase and rutile in nano-sized TiO2 by means of surface photovoltage technique and its effects on the photocatalytic activity

Photoinduced electron transfer between anatase and rutile in nanosized TiO₂, prepared by a sol–gel method, was revealed by means of the surface photovoltage technique, and its effects on the photocatalytic performance in the degradation of a phenol solution were investigated. Also, the role of the surface states during the processes of photo-physics and photochemical reactions was discussed. In the as-prepared TiO₂ sample consisting of anatase and rutile, the photoinduced electrons can easily transfer from anatase surface states to rutile, as well as from anatase conduction band to rutile. These factors are responsible for the strong surface photovoltage response and high photocatalytic activity. Moreover, the surface states related to oxygen vacancies can induce photocatalytic reactions under visible irradiation, especially in the resulting biphase TiO₂, due to the electron transfer from anatase surface states to rutile.     

Low temperature behaviour of TiO2 rutile as negative electrode material for lithium-ion batteries

High surface nanosized rutile TiO₂ is prepared via a sol-gel method from an ethylene glycol-based titanium-precursor in the presence of a non-ionic surfactant, at pH 0. Its electrochemical behaviour has been investigated at low temperature using two different potential windows. Typically, the potential window of the rutile system is 1-3 V but the use of an enlarged potential window (0.1-3 V), leads to an excellent reversible capacity of 341 mAh g⁻¹ which is comparable to graphite anodes. The electrochemical performance was investigated by cyclic voltammetry and galvanostatic techniques at temperatures ranging from −40 to 20 °C. Nanosized TiO₂ exhibits excellent rate capability (341 mAh g⁻¹ at 20 °C, 197 mAh g⁻¹ at −10 °C, 138 mAh g⁻¹ at −20 °C, and 77 mAh g⁻¹ at −40 °C at a C/5 rate) and good cycling stability. The superior low-temperature electrochemical performance of nanosized rutile TiO₂ may make it a promising candidate as lithium-ion battery material.     

TiO2 and TiO2–SiO2 thin films and powders by one-step soft-solution method: Synthesis and characterizations

Simple soft-solution method has been developed to synthesize films and powders of TiO₂ and mixed TiO₂–SiO₂ at relatively low temperatures. This method is simple and inexpensive. Furthermore, reactor can be designed for large-scale applications as well as to produce large quantities of composite powders in a single step. For the preparation of TiO₂, we used aqueous acidic medium containing TiOSO₄ and H₂O₂, which results in a peroxo-titanium precursor while colloidal SiO₂ has been added to the precursor for the formation of TiO₂–SiO₂. Post annealing at 500 °C is necessary to have anatase structure. Resulting films and powders were characterized by different techniques. TiO₂ (anatase) phase with (1 0 1) preferred orientation has been obtained. Also in TiO₂–SiO₂ mixed films and powders, TiO₂ (anatase) phase was found. Fourier transform infrared spectroscopy (FTIR) results for TiO₂ and mixed TiO₂–SiO₂ films have been presented and discussed. The method developed in this paper allowed obtaining compact and homogeneous TiO₂ films. These compact films are highly photoactive when TiO₂ is used as photo anode in an photoelectrochemical cell. Nanoporous morphology is obtained when SiO₂ colloids are added into the solution.     

Sol–gel preparation and characterization of anti-reflective and self-cleaning SiO2–TiO2 double-layer nanometric films

Glass substrates were first coated with SiO₂ and then TiO₂ by dipping into sols which were prepared by two different methods involving complex formation and hydrolysis, using ethanol (EtOH) or butyl glycol (BG). Concentration of TiO₂ in the sols was kept at 0.1 and 0.5 wt%. Prepared coatings were investigated by field-emission scanning electron microscope (FESEM), atomic force microscope (AFM), hazemeter, UV–visible spectrophotometer and goniometer. Rhodamine B (RhB) photodegradation tests were performed in order to evaluate photocatalytic activity. Application of SiO₂ as the bottom layer increased the transmittance by 6% points, thereby compensated for the loss of transmittance caused by the TiO₂ self-cleaning top layer. Pencil-hardness values of the obtained coatings were in 5B–3H range. TiO₂ coatings obtained from sols containing 0.5% TiO₂ and BG solvent represented the highest photocatalytic activity, with a rate constant of 0.44 ppm⁻¹ h⁻¹ and a half period of 5.5 h. Self-cleaning surfaces were obtained while maintaining the anti-reflectance.     

Photocatalytic H2 production from water splitting under visible light irradiation using Eosin Y-sensitized mesoporous-assembled Pt/TiO2 nanocrystal photocatalyst

Sensitized photocatalytic production of hydrogen from water splitting is investigated under visible light irradiation over mesoporous-assembled titanium dioxide (TiO₂) nanocrystal photocatalysts, without and with Pt loading. The photocatalysts are synthesized by a sol–gel process with the aid of a structure-directing surfactant and are characterized by N₂ adsorption–desorption analysis, X-ray diffraction, UV–vis spectroscopy, scanning electron microscopy, transmission electron microscopy and energy-dispersive X-ray analysis. The dependence of hydrogen production on the type of TiO₂ photocatalyst (synthesized mesoporous-assembled and commercial non-mesoporous-assembled TiO₂ without and with Pt loading), the calcination temperature of the synthesized photocatalyst, the sensitizer (Eosin Y) concentration, the electron donor (diethanolamine) concentration, the photocatalyst dosage and the initial solution pH is systematically studied. The results show that in the presence of the Eosin Y sensitizer, the Pt-loaded mesoporous-assembled TiO₂ synthesized by a single-step sol–gel process and calcined at 500 °C exhibits the highest photocatalytic activity for hydrogen production from a 30 vol.% diethanolamine aqueous solution with dissolved 2 mM Eosin Y. Moreover, the optimum photocatalyst dosage and initial solution pH for the maximum photocatalytic activity for hydrogen production are 3.33 g dm⁻³ and 11.5, respectively.     

Optical simulation of transmittance into a nanocrystalline anatase TiO2 film for solar cell applications

Optical simulation has been employed, for the first time, for rigorous evaluation of transmittance into the TiO₂ nanocrystalline film, entering from the fluorine-doped SnO₂ (F-SnO₂) coated glass side, in dye sensitized solar cells. The refractive index of the TiO₂ film with various porosities was determined theoretically, and was in agreement with the data obtained by ellipsometric measurements. The simulation clearly indicates that the transmittance into the TiO₂ film is 85–90% at 450–800 nm, on adjusting the porosity to 0.5–0.75. In contrast, transmittances experimentally determined for the TiO₂ film deposited on F-SnO₂ exhibits 70–83% at 450–800 nm, under-estimating the transmittance by about 10% compared to the simulated results. The simulation method was further substantiated by observing the high IPCE value (85% at 530 nm) for the solar cell using the same TiO₂ film sensitized by ruthenium dye.     

Development of copper-doped TiO2 photocatalyst for hydrogen production under visible light

The advantage of copper doping onto TiO₂ semiconductor photocatalyst for enhanced hydrogen generation under irradiation at the visible range of the electromagnetic spectrum has been investigated. Two methods of preparation for the copper-doped catalyst were selected – complex precipitation and wet impregnation methods – using copper nitrate trihydrate as the starting material. The dopant loading varied from 2 to 15%. Characterization of the photocatalysts was done by thermogravimetric analysis (TGA), temperature programmed reduction (TPR), diffuse reflectance UV-Vis (DR-UV-Vis), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD). Photocatalytic activity towards hydrogen generation from water was investigated using a multiport photocatalytic reactor under visible light illumination with methanol added as a hole scavenger. Three calcination temperatures were selected – 300, 400 and 500 °C. It was found that 10 wt.% Cu/TiO₂ calcined at 300 °C for 30 min yielded the maximum quantity of hydrogen. The reduction of band gap as a result of doping was estimated and the influence of the process parameters on catalytic activity is explained.     

Co-deposition of TiO2/CdS films electrode for photo-electrochemical cells

A densely packed TiO₂ thin film onto an indium doped–tin oxide (ITO) substrate was synthesized at room temperature by chemical deposition and a CdS thin film was deposited onto the pre-deposited TiO₂ film by a doctor blade route (powder of CdS was obtained from chemical deposition). TiO₂/CdS film was annealed at 300 °C for 1 h in air for crystallinity improvement. The first grown TiO₂ film was nanocrystalline, whereas the CdS film was polycrystalline as evidenced by X-ray diffraction (XRD) and selected area electron diffraction (SAED). Scanning electron microscopy (SEM) images show formation of mono-dispersed CdS spherical grains onto compact, densely packed spherical nanocrystalline grains of TiO₂. The TiO₂/CdS bilayer film was used in a photo-electrochemical cell as a working electrode, and a platinum electrode as a counter electrode (0.1 M lithium iodide electrolyte) under 80 mW/cm² light illumination intensity.     

The effect of pre-thermal treatment of TiO2 nano-particles on the performances of dye-sensitized solar cells

We have demonstrated the effect of pre-thermal treatment of TiO₂ nano-particles on the performances of dye-sensitized solar cells (DSCs) by using high specific surface area and anatase only TiO₂ nano-particles (ca. 340 m²/g, Sachtleben Chemie GmgH, represented as HK). TiO₂ particles and thin films were characterized with X-ray diffraction, FT-IR, UV–Vis diffuse reflectance spectroscopy and FE-SEM. The photoelectrochemical properties of the thin films and the performances of DSCs were measured by photocurrent densities, AC impedance spectra and photocurrent–voltage curves. Before coating the raw TiO₂ of HK (HK-raw) on transparent conducting oxide (TCO) glass for DSC fabrication, pre-thermal treatment of HK-raw by calcining at 450 °C (HK-450) was an essential step to achieve the optimum properties in terms of morphological feature, crystallinity, specific surface area and photocurrent density. HK-450 film showed the high adsorption of dye, high photocurrent density and low interface resistance between TiO₂ and TCO glass, R_TiO2/TCO and TiO₂ and redox electrolyte, R_CT, resulting in the superior photovoltaic performance on the DSC fabricated with HK-450 and Eosin Y (or ruthenium 535 bis-TBA) at AM 1.5: open-circuit voltage of 0.62 V (0.77 V), short-circuit current of 3.03 mA/cm² (22.80 mA/cm²), fill factor of 0.57 (0.44) and overall conversion efficiency of 1.06%, (7.52%). Accordingly, the optimization between the morphological feature, specific surface area and photocurrent density of TiO₂ substrate is promising to accomplish the improved overall conversion efficiency of DSC.     

The effect of temperature on the charge transport and transient absorption properties of K27 sensitized DSSC

The charge transport and transient absorption properties of K27 dye-sensitized solar cell have been investigated. The current–voltage (I–V) characteristics of the solar cell were analyzed by the thermionic emission theory. The ideality factor, barrier height and series resistance values of the solar cell were determined. The ideality factor higher than unity indicated the presence of non-ideal behavior in current–voltage characteristics at lower voltages. At the higher voltages, the charge transport mechanism for the solar cell is controlled by a space-charge limited current (SCLC) with an exponential distribution of traps. The built potential values are determined from capacitance–voltage plot and were found to be 0.14 and 0.58 V, respectively. The transient absorption data of K27 DSSC device suggest that the fast and slow phases are taking place. While the fast phase corresponds to regeneration of the dye cation by the iodide redox couple, the slow phase corresponds to the decay of long-lived I₂⁻/ TiO₂ electron absorption. The best conversion efficiency for K27 DSSC was found to be 0.317% under 100 mW/cm² (FF=0.584, V_oc=480 mV, I_sc=1.131 mA). The photocurrent results indicate that the photogeneration of charge carriers is a monophotonic process.     

Tri-layer antireflection coatings (SiO2/SiO2–TiO2/TiO2) for silicon solar cells using a sol–gel technique

Antireflection coatings (ARCs) have become one of the key issues for mass production of Si solar cells. They are generally performed by vacuum processes such as thermal evaporation, reactive sputtering, and plasma-enhanced chemical vapor deposition. In this work, a sol–gel method has been demonstrated to prepare the ARCs for the non-textured monocrystalline Si solar cells. The spin-coated TiO₂ single-layer, SiO₂/TiO₂ double-layer and SiO₂/SiO₂–TiO₂/TiO₂ triple-layer ARCs were deposited on the Si solar cells and they showed good uniformity in thickness. The measured average optical reflectance (400–1000 nm) was about 9.3, 6.2 and 3.2% for the single-layer, double-layer and triple-layer ARCs, respectively. Good correlation between theoretical and experimental data was obtained. Under a triple-layer ARC condition, a 39% improvement in the efficiency of the monocrystalline Si solar cell was achieved. These indicate that the sol–gel ARC process has high potential for low-cost solar cell fabrication.     

Improved photon management in a photoelectrochemical cell with Nd-modified TiO2 thin film photoanode

Photon management involving particularly an up-conversion process is proposed as a relatively novel strategy for improving the efficiency of hydrogen generation in photoelectrochemical cells (PEC) with wide-band gap photoanodes. Optically active photoanode has been constructed by electrodeposition of titanium dioxide nanopowders containing Nd³⁺ ions, synthesized via a sol-gel method, onto ITO/TiO₂(thin film) substrates. Thin films of TiO₂ have been deposited by means of RF magnetron sputtering in an ultra-high-vacuum system. X-ray diffraction, scanning electron microscopy, UV-VIS-NIR spectrophotometry, and photoluminescence have been applied to assess the properties of photoanodes. In experiments involving photon-assisted water splitting, an external up-converter containing Yb³⁺/Er³⁺ rare-earth ions has been used. Photocurrent as a function of voltage (V_B) under illumination with white light is relatively high (280 μA at V_B = 0 V) for pure TiO₂ thin films and it is not affected by the electrodeposition of TiO₂:Nd³⁺ powders. NIR-driven up-conversion with laser excitation at λ = 980 nm has been found responsible for a 13-fold increase in photocurrent at V_B = 0 V in the modified PEC configuration.     

Enzymatic hydrogen production by light-sensitized anodized tubular TiO2 photoanode

Preliminary experiments with a slurry system of enzyme and powdery photocatalyst mixed in one compartment suggested that the electron transfer from light-sensitized photocatalyst to enzyme is the rate-determining step. Hence, in this study an anodized tubular TiO₂ electrode (ATTE) on a titanium substrate was examined as a photoanode in an anodic cell for enzymatic hydrogen production in a cathodic cell. Anodization of Ti foil in a two-electrode electrochemical cell followed by annealing in an O₂ atmosphere led to the formation of a tube-shaped TiO₂ arrays, destroyed tube arrays, or spongelike TiO₂ dense film. Samples were proven based on methylene blue (MB) discoloration to be photocatalytically active. The rate of photocatalytic hydrogen production in one of the samples (20 V–25 °C in a mixed electrolyte/350 °C–5 h) was 40 μmol/(h cm²) with a 0.1 M Na₂S electrolyte in one compartment reactor system, while the enzymatic hydrogen production rate with light-sensitized photoanode was 30 μmol/(h cm²) in the cathodic compartment with an oxygen production rate of 15 μmol/(h cm²) in the anodic compartment. These results confirmed the successful evolution of stoichiometric H₂ and O₂ separately. For the system with a sample (20 V–5 °C in 0.5% HF/650 °C–5 h), a hydrogen production rate was ca. 43 μmol/(h cm²) in the cathodic compartment and an oxygen production rate was ca. 20 μmol/(h cm²) in the anodic compartment. X-ray diffraction (XRD) results clearly indicated that the samples showing the highest evolution rate were composed of both anatase and rutile, while those made of either anatase or rutile showed a lower evolution rate. Higher annealing temperatures increased the thickness of the oxide barrier layer and obstructed the charge transfer to the back contact.