Quasi-solid-state dye-sensitized solar cells employing nanocrystalline TiO2 films made at low temperature

Quasi-solid-state dye-sensitized solar cells with enhanced performance were made by using nanocrystalline TiO₂ films without any template deposited on plastic or glass substrates at low temperature. A simple and benign procedure was developed to synthesize the low-temperature TiO₂ nanostructured films. According to this method, a small quantity of titanium isopropoxide (TTIP) was added in an ethanolic dispersion of TiO₂ powder consisting of nanoparticles at room temperature, which after alkoxide's hydrolysis helps to the connection between TiO₂ particles and to the formation of mechanically stable thick films on plastic or glass substrates. Pure TiO₂ films without any organic residuals consisting of nanoparticles were formed with surface area of 56 m²/g and pore volume of 0.383 cm³/g similar to that obtained for Degussa-P25 powder. The structural properties of the films were characterized by microscopy techniques, X-ray diffractometry, and porosimetry. Overall solar to electric energy conversion efficiencies of 5.3% and 3.2% (under 1sun) were achieved for quasi-solid-state dye-sensitized solar cells employing such TiO₂ films on F:SnO₂ glass and ITO plastic substrates, respectively. Thus, the quasi-solid-state device based on low-temperature TiO₂ attains a conversion efficiency which is very close to that obtained for cells consisting of TiO₂ nanoparticles sintered at high temperature.     

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.     

Effective water splitting using N-doped TiO2 films: Role of preferred orientation on hydrogen production

N-doped TiO₂ film with preferred (211) orientation, deposited by RF magnetron sputtering, was investigated for the water-splitting hydrogen production. It is found that the preferred crystal growth orientation of the films can be controlled by N₂ flow rate during the deposition. The results reveal that not only the N-doping, but also the preferred orientation (i.e., large percentage of exposed (211) facet), can effectively enhance the activity of TiO₂-based photocatalyst. With the increase of exposed (211) facets, the hydrogen production rates of N-doped TiO₂ films rise from 760 μmol H₂ h⁻¹ m⁻² to 4500 μmol H₂ h⁻¹ m⁻², indicating that high performance of TiO₂-based photocatalyst can be achieved by controlling the preferred orientation of the films.     

Electrochromic properties of heat-treated thin films of CeO2–TiO2–ZrO2 prepared by sol–gel route

CeO₂–TiO₂–ZrO₂ thin films were prepared using the sol–gel process and deposited on glass and ITO-coated glass substrates via dip-coating technique. The samples were heat treated between 100 and 500 °C. The heat treatment effects on the electrochromic performances of the films were determined by means of cyclic voltammetry measurements. The structural behavior of the film was characterized by atomic force microscopy and X-ray diffraction. Refractive index, extinction coefficient, and thickness of the films were determined in the 350–1000 nm wavelength, using nkd spectrophotometry analysis.Heat treatment temperature affects the electrochromic, optical, and structural properties of the film. The charge density of the samples increased from 8.8 to 14.8 mC/cm², with increasing heat-treatment temperatures from 100 to 500 °C. It was determined that the highest ratio between anodic and cathodic charge takes place with increase of temperature up to 500 °C.     

Highly-efficient electrochromic performance of nanostructured TiO2 films made by doctor blade technique

Electrochromic TiO₂ anatase thin films on F-doped tin oxide (FTO) substrates were prepared by doctor blade method using a colloidal solution of titanium oxide with particles of 15 nm in size. The films were transparent in the visible range and well colored in a solution of 1 M LiClO₄ in propylene carbonate. The transmittances of the colored films were found to be strongly dependent on the Li⁺ inserted charges. The response time of the electrochromic device coloration was found to be as small as 2 s for a 1 cm² sample and the coloration efficiency at a wavelength of 550 nm reached a value as high as 33.7 cm² C⁻¹ for a 600 nm thick nanocrystalline-TiO₂ on a FTO-coated glass substrate. Combining the experimental data obtained from in situ transmittance spectra and in situ X-ray diffraction analysis with the data from chronoamperometric measurements, it was clearly demonstrated that Li⁺ insertion (extraction) into (out of) the TiO₂ anatase films resulted in the formation (disappearance) of the Li_0.5TiO₂ compound. Potential application of nanocrystalline porous TiO₂ films in large-area electrochromic windows may be considered.     

Silver/titania nanocomposite-modified photoelectrodes for photoelectrocatalytic methanol oxidation

Silver deposited titania (Ag/TiO₂) nanocomposite thin films were fabricated by the simple sonochemical deposition of Ag on preformed aerosol-assisted chemical vapor deposited TiO₂ thin films. The photelectrocatalytic performance of a newly fabricated Ag/TiO₂-modified photoelectrode was studied for methanol oxidation under simulated solar AM 1.5G irradiation (100 mW/cm²). The Ag/TiO₂-modified photoelectrode showed a photocurrent density of 1 mA/cm², which is four times that of an unmodified TiO₂ photoelectrode. The modification of Ag on the TiO₂ surface significantly enhanced the photoelectrocatalytic performance by improving the interfacial charge transfer processes, which minimized the charge recombination. Density functional theory (DFT) calculation studies revealed that methanol could be easily adsorbed onto the Ag surfaces of Ag/TiO₂ via a partial electron transfer from Ag to methanol. The newly fabricated Ag/TiO₂-modified photoelectrode could be a promising candidate for photoelectrochemical applications.     

Influence of surfactants on Fe2O3 nanostructure photoanode

Fe₂O₃ nanostructures photoanodes were prepared via sol–gel spin-coating method onto fluorine-doped tin oxide glass substrates using six different surfactants: polyethylene glycol (PEG-300), Triton X-100, pluronic F127, cetyltrimethylammonium bromide (CTAB), octadecyltrimethylammonium bromide (OTAB) and tetradecyltrimethylammonium bromide (TTAB). The resulting films have thickness from 520 ± 10 to 980 ± 10 nm after calcinations at 450 °C in the air. A comparative study of photocatalytic activity of thin films was performed. The photo-generated samples were determined by measuring the currents and voltages under illumination of UV–vis light. The highest photocurrent density of 1.77 mA/cm² at 1 V/SCE, under illumination intensity of 100 mW cm⁻² from a solar simulator with a global AM 1.5 filter, were produced by TTAB treated sample. The optical properties, morphology, surface roughness and structure of the films were also characterized by UV–visible spectroscopy, SEM, AFM and XRD. The results are consistent with photocatalytic performance: TTAB treated sample has the highest grain size and optical absorption. The improved performance of this sample can be attributed to the crystallinity process of TTAB, which leads to the larger grain size and highest photocatalytic activity. The study demonstrates that photoelectrochemical performance of metal oxide can be improved by simply changing surfactant. The results highlighted the superior performance of cationic surfactants over non-ionic surfactants in preparing Fe₂O₃ photoanodes by sol–gel method. Moreover, the study showed that decreasing hydrocarbon tail of cationic surfactants can increase the crystallite size and improve photocatalytic activity.     

Hydrogen production by photocatalytic membranes fabricated by supersonic cluster beam deposition on glass fiber filters

Photoactive membranes coated with TiO₂ and Pt/TiO₂ nanostructured thin films were produced by one-step deposition of gas phase nanoparticles on glass fiber filters. Pt/TiO₂ nanoparticles (0–1.5 wt.% Pt content) were produced by flame spray pyrolysis, starting from liquid solutions of the Ti and Pt precursors, and then expanded in a supersonic beam to be deposited on the filters. The nanostructured coatings were composed of crystalline nanoparticles (mainly anatase phase), without any need of post-deposition annealing. The so obtained photocatalytic membranes were tested in hydrogen production by photo-steam reforming of ethanol in an expressly set-up diffusive photoreactor. The reaction rate was found to increase with increasing the Pt content in the photoactive material, up to 1.5 wt.% Pt. The use of these membranes allowed a significant increase of the hydrogen production rate compared to that obtained with the same photoactive Pt/TiO₂ films deposited on a quartz substrate.     

Ultrathin hematite films deposited layer-by-layer on a TiO2 underlayer for efficient water splitting under visible light

Ultrathin hematite (α-Fe₂O₃) film deposited on a TiO₂ underlayer as a photoanode for photoelectrochemical water splitting was described. The TiO₂ underlayer was coated on conductive fluorine-doped tin oxide (FTO) glass by spin coating. The hematite films were formed layer-by-layer by repeating the separated two-phase hydrolysis-solvothermal reaction of iron(III) acetylacetonate and aqueous ammonia. A photocurrent density of 0.683 mA cm⁻² at +1.5 V vs. RHE (reversible hydrogen electrode) was obtained under visible light (>420 nm, 100 mW cm⁻²) illumination. The TiO₂ underlayer plays an important role in the formation of hematite film, acting as an intermediary to alleviate the dead layer effect and as a support of large surface areas to coat greater amounts of Fe₂O₃. The as-prepared photoanodes are notably stable and highly efficient for photoelectrochemical water splitting under visible light. This study provides a facile synthesis process for the controlled production of highly active ultrathin hematite film and a simple route for photocurrent enhancement using several photoanodes in tandem.     

Photoelectric properties of BiVO4 thin films deposited on fluorine doped tin oxide substrates by a modified chemical solution deposition process

BiVO₄ films deposited on Fluorine doped tin oxide glass substrates were successfully prepared by a modified chemical solution deposition process. Structure and optical spectrum analysis show that the resultant BiVO₄ films consist entirely of monoclinic scheelite structure and have a narrow band gap of ～2.66 eV. The films were investigated by photoelectrochemical and photovoltaic measurements with regard to hydrogen production and solar energy conversion under visible light. The BiVO₄ photoanodes show significantly higher visible light induced photoelectrochemical performance (～1.1 mA/cm² at 1.0 V vs. Ag/AgCl) than those reported ones, which is very promising for splitting water to H₂ and O₂. A Schottky BiVO₄ solar cell was also investigated for comparison with photoelectrochemical measurements. The correlation between the photoelectrochemical and photovoltaic behavior for BiVO₄ was explained. Our research should provide important support for the applications of BiVO₄ films or its modified forms such as doping and nanocomposite in heterojunction photoelectrochemical cells and solar cells with suitable energy level alignment at the interface.     

The effects of hydrothermal temperature and thickness of TiO2 film on the performance of a dye-sensitized solar cell

The effects of hydrothermal temperature on the preparation of TiO₂ colloids, and their film thickness on fluorine-doped tin oxide (FTO) glass, toward the performance of a dye-sensitized solar cell (DSSC) were investigated. Pore diameter and surface area of the TiO₂ are of paramount importance in determining the cell efficiency. With the increase of hydrothermal temperature, the pore diameter increases linearly; however, the surface area shows the reverse effect. It is found that the DSSC assembled with the TiO₂ films prepared under the hydrothermal temperature of 240 °C, and the film thickness larger than 10 μm gives optimal performance. The effect of film thickness of TiO₂ on the performance of the DSSC can be explained by the relative size of reactive species diffusing into the thin film and the lifetime of injected electrons. Electrochemical impedance spectroscopy (EIS) was also used to analyze the resistance of the cell, developed as a result of the change in the thickness of the TiO₂ thin film. The at-rest stability for over 200 days was monitored and the results show that the solar energy conversion efficiency was found to decrease from 5.0% of initial value to 3.0% at the end.     

TiO2 thin films as protective material for transparent-conducting oxides used in Si thin film solar cells

Nb-doped TiO₂ films have been fabricated by RF magnetron sputtering as protective material for transparent-conducting oxide (TCO) films used in Si thin film solar cells. It is found that TiO₂ has higher resistance against hydrogen radical exposure, utilizing the hot-wire CVD (catalytic CVD) apparatus, compared with SnO₂ and ZnO. Further, the minimum thickness of TiO₂ film as protective material for TCO was experimentally investigated. Electrical conductivity of TiO₂ in the as-deposited film is found to be 10⁻⁶ S/cm due to the Nb doping. Higher conductivity of 10⁻² S/cm is achieved in thermally annealed films. Nitrogen treatments of Nb-doped TiO₂ film have been also performed for improvements of optical and electric properties of the film. The electrical conductivity becomes 4.5×10⁻² S/cm by N₂ annealing of TiO₂ films at 500 °C for 30 min. It is found that the refractive index n of Nb-doped TiO₂ films can be controlled by nitrogen doping (from n=2.2 to 2.5 at λ = 550 nm) using N₂ as a reactive gas. The controllability of n implies a better optical matching at the TCO/p-layer interface in Si thin film solar cells.     

Hydrogen generation from photocatalytic water splitting over TiO2 thin film prepared by electron beam-induced deposition

Photocatalytic TiO₂ thin films were prepared via an electron beam-induced deposition (EBID) method. The effects of post-calcination treatment on the properties of the prepared TiO₂ thin films were studied. X-ray diffraction (XRD), scanning electron microscope-energy dispersive spectrometry (SEM-EDS), and UV–V is absorption spectrometry were performed to reveal the crystallinity, surface morphology, chemical composition, and light absorbance of the prepared TiO₂ thin films. The photoelectrochemical characteristics of the TiO₂ thin films were investigated with a potentiostat. Under UV irradiation, a photocurrent of ˜2.1 mA was observed for the TiO₂ thin film with post-calcination at 500 °C. A water-splitting reaction was conducted over the TiO₂ thin film with the best photoelectrochemical performance. The yields of hydrogen and oxygen were 59.8 and 30.6 μmole, respectively, after 8 h of reaction under UV irradiation.     

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 oxidation on nanostructured chalcogenide modified titanium dioxide

Surface mesoscopic titanium dioxide (P25) films deposited onto conducting glass plates (SnO₂:F) were modified by colloidal Ru_xSe_y nanoparticles (2 nm diameter). A decrease of the photocurrent was found upon modification of TiO₂ films. However, interfacial electron transfer kinetics to oxygen was favored. The increase of the catalyst surface concentration onto TiO₂, shifts the onset of the photocurrent under UV-illumination, to 0.6 V/RHE in presence of oxygen dissolved in the electrolyte. Concomitant to this, the cathodic current becomes important and shifts to more positive potentials. This phenomenon allows the system to work catalytically under open circuit conditions. On non-modified TiO₂, the application of a 0.3 V/RHE potential leads to an enhancement of the photooxidation of formic acid. Photocurrent images revealed a non-homogeneous distribution of the catalyst on the titanium dioxide films.     

Optical and structural properties of TiO2 thin films prepared by sol-gel spin coating

Hydrogen is a renewable and non-polluting fuel. Its production from water using renewable energy is an attractive challenge. In this work we report some results on the preparation of titanium oxide TiO₂ thin films for environmental applications such as water photosplitting. TiO₂ thin films have been prepared by spin coating technique of sol precursor onto glass substrates. The deposited films were annealed at different temperatures in air. The X-ray diffraction (XRD) experiments show that the two well-known anatase and rutile phases were observed depending both on the conditions of deposition and on the temperature of annealing. The best conditions of crystallization were found to be around 400 °C in air. The influence of the number of deposited layer on the crystalline quality of the films was investigated. The surface morphology of the deposited film was characterized by atomic force microscopy (AFM) and scanning electronic microscopy (SEM). The UV-Vis-NIR spectroscopy shows that the film exhibits a high transmission around 90%. The best layers were obtained when concentrated (HCl) was added to the sol solutions. The direct band gap of the films was found to be around 3.7 eV, and their refractive index was found to vary from 2 to 2.4.     

Ternary AgInSe2 film electrode created using selenization of RF magnetron sputtered Ag–In metal precursor for photoelectrochemical applications

AgInSe₂ ternary semiconductor thin films are deposited on glass substrates and indium-doped-tin-oxide (ITO)-coated glass substrates using the selenization of magnetron sputtered Ag–In metal precursors. X-ray diffraction (XRD) and energy-dispersive analysis of X-ray (EDAX) results show that the crystal phase of samples changed from AgInSe₂ to a solid mixture of AgInSe₂ and Ag₂Se with a decrease in the [In]/[In + Ag] molar ratio in samples. The direct and indirect energy band gaps of the samples vary in the ranges of 1.27–1.45 eV and 0.91–1.17 eV, respectively, depending on the [In]/[In + Ag] molar ratio in samples. The flat-band potentials of samples are in the range of −0.47 to −0.71 V (vs. normal hydrogen electrode) in a solution containing Na₂S (0.35 M) + K₂SO₃ (0.25 M) obtained using Mott–Schottky measurements. The maximum photocurrent density of the samples on ITO-coated glass substrates is 31.7 mA/cm² at an external potential of +1.0 V (vs. Ag/AgCl) in the solution containing Na₂S (0.35 M) + K₂SO₃ (0.25 M) ions.     

Effect of the sintering temperature on the photocatalytic activity of ZnO+Zn2TiO4 thin films

ZnO+Zn₂TiO₄ thin films were obtained by the sol–gel method, the precursor solutions were prepared using two Ti/Zn ratios: 0.49 and 0.69. The films were deposited on glass slide substrates and sintered at temperatures in the 200–600 °C range in increments of 50 °C, with the goal of studying the dependence of the photocatalytic activity (PA) on the annealing temperature. The films were characterized by X-ray diffraction and UV–Vis spectroscopy. The PA was evaluated by measuring the UV–Vis absorption spectra of the methylene blue in aqueous solution before and after photobleaching, using the Lambert–Beer's principle. The higher photocatalytic activities were obtained from the films with sintering temperature around 450 °C, for both Ti/Zn ratios studied.     

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.     

Efficient indium tin oxide/Cr-doped-TiO2 multilayer thin films for H2 production by photocatalytic water-splitting

Cr-doped-TiO₂ thin films, with three different Cr concentrations (2, 5.5, and 9 at.%), have been synthesized by radio-frequency magnetron sputtering in order to sensitize TiO₂ in visible light. UV–visible spectra showed that maximum narrowing (2.1 eV) of the TiO₂ band gap is obtained for the highest Cr concentration. However, negligible photocurrent was measured with Indium Tin Oxide (ITO)/Cr-doped-TiO₂ (9 at.%) single bilayer sample due to the increased recombination rate of the photo-generated charges on the defects associated to the Cr³⁺ ions. To lower the charge recombination rate in the Cr-doped-TiO₂, multilayer films with different numbers of ITO/Cr-doped-TiO₂ (9 at.%) bilayers (namely, 3-, 4-, 5-, 6- and 7-bilayers) were deposited by keeping the total thickness of TiO₂ constant in each multilayer film. When the multilayer films were exposed to visible light, we observed that the photocurrent increases as function of the number of bilayers by reaching the maximum with 6-bilayers of ITO/Cr-doped-TiO₂. The enhanced photocurrent is attributed to: 1) higher absorption of visible light by Cr-doped-TiO₂, 2) number of space charge layers in form of ITO/TiO₂ interfaces in multilayer films, and 3) generation of photoelectrons just in/or near to the space charge layer by decreasing the Cr-doped-TiO₂ layer thickness. The reduced charge recombination rate in multilayer films was also confirmed by studying the photocurrent kinetic curve. The superior photocatalytic efficiency of the 6-bilayers film implies higher hydrogen production rate through water-splitting: we obtained indeed 24.4 μmol/h of H₂ production rate, a value about two times higher than that of pure TiO₂ (12.5 μmol/h).