Efficiency improvement of dye-sensitized solar cells based on electrodeposited TiO2 films by low temperature post-treatment

Porous crystalline TiO₂ films can be prepared at low temperatures (80 °C) by surfactant-assisted electrodeposition from TiCl₃ solution. Nevertheless, up to now calcination at high temperatures (typically 450 °C) was still necessary to establish a good performance of these films in dye-sensitized solar cells (DSSC). With this study we report that water vapour treatment at much lower temperatures (150 °C) for 1 week improves the performance of the films in DSSC to the same degree as calcination although the overall crystallinity remains lower. Reason for the good efficiency is that the porous structure stays intact and thus the dye molecules can be better adsorbed. Avoiding high temperatures during the preparation process of TiO₂ films for the application in DSSC enables the use of polymer substrates for the fabrication of flexible solar cells.     

TiO2-B narrow nanobelt/TiO2 nanoparticle composite photoelectrode for dye-sensitized solar cells

In order to possess the merits of both building blocks, i.e. the rapid interfacial electron transport of TiO₂-B narrow nanobelts (NBs) and the high surface area of TiO₂ nanoparticles (NPs), the TiO₂-B NBs and TiO₂ NPs composites photoelectrodes were prepared with different weight ratios. The dye-sensitized solar cell prototypes were fabricated based on the composite photoelectrodes and the photoelectrical properties have been systematically studied. Although the amount of adsorption dye of composite solar cells decreased, the composite cells could obtain higher power conversion efficiency compared to pure TiO₂ NP solar cell by rational tuning the weight ratio of TiO₂-B NBs and TiO₂ NPs, which was due to the faster electron transfer rate. The dye adsorption amount and interfacial electron transport, which together determined the overall photoelectrical conversion efficiency, were investigated by the UV–vis spectra, the electrochemical impedance spectra (EIS), intensity-modulated photocurrent spectroscopy (IMPS) and intensity-modulated photovoltage spectroscopy (IMVS).     

Synthesis of Zn-doped TiO2 microspheres with enhanced photovoltaic performance and application for dye-sensitized solar cells

Zn-doped TiO₂ microspheres have been synthesized by introducing a trace amount of zinc nitrate hexahydrate to the reaction system. Scanning electron microscope (SEM), field-emission scanning electron microscope (FESEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) have been utilized to characterize the samples. Both surface photovoltage spectroscopy (SPS) technique based on lock-in amplifier and transient photovoltage (TPV) measurement reveal that the slight doping of Zn can promote the separation of photo-generated charges as well as restrain the recombination due to the strong interface built-in electric field and the decreasing of surface trap states. The photovoltaic parameters of dye-sensitized solar cells (DSSCs) based on Zn-doped TiO₂ are significantly better, compared to that of a cell based on undoped TiO₂. The relation between the performance of DSSCs and their photovoltaic properties is also discussed.     

Enhancing the performance of dye-sensitized solar cells based on an organic dye by incorporating TiO2 nanotube in a TiO2 nanoparticle film

The photoelectrochemical properties of a high molar extinction coefficient charge transfer organic dye containing thienylfluorene segment called FL, and the effect of incorporating TiO₂ nanotube (TiNT) in TiO₂ nanoparticle film along with the above dye on the photovoltaic performance of dye-sensitized solar cells (DSSCs) were investigated. The influence of soaking time of the TiO₂ electrode in dye solution and the effect of varying its concentration, on the solar cell efficiency was also studied. Cyclic voltammetric (CV) analysis revealed the linear relationship between the anodic peak current and the scan rate, indicating a surface-confined diffusion process.The surface morphology of TiNT was characterized using SEM, TEM and XRD. The open-circuit voltage (V_OC) of the DSSC increased with the increase in the wt% of TiNT and shows optimal value at about 5 wt%, which is correlated with the suppression of the electron recombination as found out from the electron lifetime studies.The electrochemical impedance spectroscopy (EIS) technique was employed to quantify the charge transport resistance (R_ct) and electron lifetime under different ratios of the TiNT/nanoparticle. The electron lifetimes of the DSSCs based on FL and N3 dye were very close to one another and the DSSC based on the FL showed respectable photovoltaic performance of ca. 7.8% under the light intensity of 100 mW cm⁻² (AM 1.5G).     

Anatase TiO2 spheres with high surface area and mesoporous structure via a hydrothermal process for dye-sensitized solar cells

Spherical pure anatase TiO₂ spheres with a mesoporous structure and high surface area of up to 116.5 m² g⁻¹ were prepared by a simple urea-assisted hydrothermal process and investigated as dye-sensitized solar-cell electrodes. Although the particle diameters of the prepared TiO₂ spheres ranged from 0.4 to 1.3 μm, due to the high specific surface area, mesoporous TiO₂ sphere electrode was obtained with enhanced light harvesting and a larger amount of dye loading. An overall light conversion efficiency of 7.54% under illumination of simulated AM 1.5G solar light (100 mW cm⁻²) was achieved using the mesoporous TiO₂ spheres electrode, which was significantly higher than a commercial Degussa P25 TiO₂ nanocrystals electrode (5.69%).     

Dye-sensitized solar cells based on double-layered TiO2 composite films and enhanced photovoltaic performance

Dye-sensitized solar cells (DSSCs) are fabricated based on double-layered composite films of TiO₂ nanoparticles and hollow spheres. The photoelectric conversion performances of DSSCs based on nanoparticles/nanoparticles (PP), hollow spheres/hollow spheres (HH), hollow spheres/nanoparticles (HP), and nanoparticles/hollow spheres (PH) double-layered films are investigated, and their photo-electric conversion efficiencies are 4.33, 4.72, 4.93 and 5.28%, respectively. The enhanced performance of TiO₂ nanoparticles/hollow spheres double-layered composite film solar cells can be attributed to the combined effect of following factors. The light scattering of overlayer hollow spheres enhances harvesting light of the DSSCs and the underlayer TiO₂ nanoparticle layer ensures good electronic contact between film electrode and the F-doped tin oxide (FTO) glass substrate. Furthermore, the high surface areas and pore volume of TiO₂ hollow spheres are respectively beneficial to adsorption of dye molecules and transfer of electrolyte solution.     

Conversion enhancement of flexible dye-sensitized solar cells based on TiO2 nanotube arrays with TiO2 nanoparticles by electrophoretic deposition

We prepared highly ordered titanium dioxide nanotube arrays (TNAs) by anodizing Ti foils in F⁻ containing electrolyte. The thickness and dye loading amount of TNAs were 26 μm and 1.06 × 10⁻⁷ mol cm⁻², respectively. TiO₂ nanoparticles (TNPs) were electrophoretically deposited on the inner wall of nanotube to produce coated nanotube arrays (TNAP). The dye loading was increased to 1.56 × 10⁻⁷ mol cm⁻², and the electron transport rate improved. TNAs and TNAP were sensitized with ruthenium dye N3 to yield dye-sensitized TiO₂ nanotube solar cells. The power conversion efficiency of TNA-based dye-sensitized solar cells (DSSCs) was 4.28%, whereas the efficiency of TNAP-based DSSCs increased to 6.28% when illuminated from the counter electrode. The increase of power conversion efficiency of TNAP-based DSSCs is ascribed to the increased surface area of TNAs and the faster electron transport rate.     

Al2O3-coated SnO2/TiO2 composite electrode for the dye-sensitized solar cell

A novel Al₂O₃-coated SnO₂/TiO₂ composite electrode has been applied to the dye-sensitized solar cell. In such an electrode, two kinds of energy barriers (SnO₂/TiO₂ and TiO₂/Al₂O₃) were designed to suppress the recombination processes of the photo-generated electrons and holes. After the SnO₂ was modified by colloid TiO₂, the photoelectric conversion efficiency of the SnO₂/TiO₂ composite cell increased to 2.08% by a factor of 2.8 comparing with that of the SnO₂ cell. The Al₂O₃ layer on the SnO₂/TiO₂ composite electrode further suppressed the generation of the dark current, resulting in 37% improvement in device performance comparing with the SnO₂/TiO₂ cell.     

Cationic surfactant promoted reductive electrodeposition of nanocrystalline anatase TiO2 for application to dye-sensitized solar cells

A new strategy involving the introduction of the common cationic surfactant cetyltrimethylammonium bromide (CTAB) for the cathodic deposition of titanium dioxide from hydrolyzed TiCl₄ and TiCl₃ solutions by cyclic voltammetry has been developed. Crack-free and non-transparent anatase TiO₂ films were obtained for the first time and characterized with the aid of Raman spectra and SEM. Selection of TiCl₄ as the precursor for the electrodeposition is quite a novel approach for the research in the area of dye-sensitized solar cells (DSSCs). It is noted that NO₃⁻ ion is essential for such a deposition. Under the same conditions, a thicker TiO₂ film was obtained by adding CTAB into KNO₃ electrolyte, compared with the case without it. The CTAB-promoted film led to an increased energy conversion efficiency of the corresponding DSSC. Mechanisms are proposed for the electrochemical deposition and the beneficial role of CTAB.     

Titanium flexible photoanode consisting of an array of TiO2 nanotubes filled with a nanocomposite of TiO2 and graphite for dye-sensitized solar cells

A flexible dye-sensitized solar cell (DSSC) was fabricated using a photoanode consisting of an array of TiO₂ nanotubes (TNT) filled with a nanocomposite of TiO₂ (P90) and nanographite. The array of TNT was obtained by anodic oxidation of Ti foil, and this Ti foil with TNT was used as the photoanode of the DSSC. Each tube in the array has an average diameter of 100 nm. The morphologies of the array of TNT were obtained both after and before filling them with the TiO₂/graphite nanocomposite, using a field-emission scanning electron microscopy (FE-SEM). DSSC with photoanode consisting of the nanocomposite (photoanode designated as Graphite/P90-TNT) rendered a light-to-electricity conversion efficiency (η) of 5.75%. In contrast, the cells with photoanodes consisting of only TNT (photoanode designated as TNT) and TNT filled with P90-TiO₂ (photoanode designated as P90-TNT) exhibited efficiencies (η) of 4.44% and 5.14%, respectively. The enhancements in the η’s in favor of the cells with P90-TNT and Graphite/P90-TNT were attributed to the filled P90 and nanocomposite, respectively. The filled particles were assumed to provide more conductive pathways for electron transfer and prolonged lifetime for electrons in the film of TNT. The results were substantiated by light-absorption values, incident-photo-to-current efficiency (IPCE) curves, Nyquist and Bode plots of electrochemical impedance spectroscopy (EIS), and photopotential transient curves.     

Photovoltaic performance improvement of dye-sensitized solar cells based on tantalum-doped TiO2 thin films

Dye-sensitized solar cells based on a tantalum (Ta)-doped TiO₂ thin film prepared by the hydrothermal method show a photovoltaic efficiency of 8.18%, which is higher than that of the undoped TiO₂ thin film (7.40%). The Mott-Schottky plot indicates that the Ta-doped TiO₂ photoanode shifts the flat band potential positively and increases the electron density. The positive shift of the flat band potential improves the driving force of injected electrons from the LUMO of the dye to the conduction band of TiO₂. Furthermore, the increased electron density caused by the Ta-doped TiO₂ improves the fill factor of the solar cell. The increased electron density accelerates the transfer rate of electrons in the Ta-doped TiO₂ thin films by comparison to undoped films, which is confirmed by intensity-modulated photocurrent spectroscopy measurements.     

Electrophoretic deposition of nanocrystalline TiO2 films on Ti substrates for use in flexible dye-sensitized solar cells

Nanocrystalline TiO₂ films were prepared on flexible Ti-metal sheets by electrophoretic deposition followed by chemical treatment with tetra-n-butyl titanate (TBT) and sintering at 450 °C. X-ray diffraction (XRD) analysis indicates that TBT treatment led to the formation of additional anatase TiO₂, which plays an important role in improving the interconnection between TiO₂ particles, as well as the adherence of the film to the substrate, and in modifying the surface properties of the nanocrystalline particles. The effect of TBT treatment on the electron transport in the nanocrystalline films was studied by intensity-modulated photocurrent spectroscopy (IMPS). An increase in the conversion efficiency was obtained for the dye-sensitized solar cells with TBT-treated nanocrystalline TiO₂ films. The cell performance was further optimized by designing nanocrystalline TiO₂ films with a double-layer structure composed of a light-scattering layer and a transparent layer. The light-scattering effect of the double-layer nanocrystalline films was evaluated by diffuse reflectance spectra. Employing the double-layer nanocrystalline films as the photoelectrodes resulted in a significant improvement in the incident photo-to-current conversion efficiency of the corresponding cells due to enhanced solar absorption by light scattering. A high conversion efficiency of 6.33% was measured under illumination with 100 mW cm⁻² (AM 1.5) simulated sunlight.     

EIS analysis of hydrophobic and hydrophilicTiO2 film

Titanium oxide films were formed on metallic titanium substrates by employing a thermal treatment at 800 °C under air atmosphere. Component and microstructure of the oxide films were characterized by XRD and SEM method. Water contact angles on titanium oxide film surface were measured in both dark and sunlight illumination condition. Corrosion tests were carried in seawater solution under different illuminate conditions. Electrochemical impedance spectroscopy (EIS) techniques were used to study the changes on TiO₂ film. Results indicated that: hydrophilic TiO₂ film suffered a severe photo-corrosion effect in seawater due to their semiconductor properties under sunlight condition, but the hydrophobic TiO₂ film under dark condition exhibited a good corrosion resistance.     

A natural tomato slurry as a photosensitizer for dye-sensitized solar cells with TiO2/CuO composite thin films

We have studied the performance of dye-sensitized solar cells by employing natural dye “anthocyanins” extracted from the tomato slurry as a sensitizer for the TiO₂/CuO photoanode. The extracts were anchored on TiO₂/CuO films deposited on an ITO substrate which was used as a photoanode. The dye adsorbed TiO₂/CuO films electrode, the copper plate as a counter electrode, and iodolyte as an electrolyte were assembled into DSSCs. The conversion efficiency of the DSSCs was found to be 2.96% with a V_OC of 0.615 V, J_SC of 6.6 mA/cm², and an FF of 0.73. This work highlights the use of contribution of the tomato slurry as a natural sensitizer to enhance the efficiency of DSSCs.     

TiO2/modified natural clay semiconductor as a potential electrode for natural dye-sensitized solar cell

TiO₂/modified natural bentonite clay semiconductor, as a potential electrode of dye-sensitized solar cell, having a Ti:Si molar ratio of 85:15 was, for the first time, compared with pure TiO₂ (commercial P25) electrode in terms of solar cell efficiency and characteristics. 4-Chloro-2,5-difluorobenzoic acid and 4-(chloromethyl)benzoyl chloride were added to the electrodes to increase light harvesting ability of natural dyes extracted from red cabbage, rosella, and blue pea. The results showed that the TiO₂/clay semiconductor provided a higher surface area but a slightly lower efficiency than the pure TiO₂. The best natural sensitizer was found to be the dye extracted from red cabbage. Besides, the 4-(chloromethyl)benzoyl chloride provided a higher short circuit current for the TiO₂/clay semiconductor.     

An efficient and low-cost TiO2 compact layer for performance improvement of dye-sensitized solar cells

A TiO₂ organic sol was synthesised for the preparation of a compact TiO₂ layer on fluorine-doped tin oxide (FTO) glass by a dip-coating technique. The resultant thin film was used for the fabrication of dye-sensitized solar cells (DSSCs). The compact layer typically has a thickness of ca. 110 nm as indicated by its SEM, and consists of anatase as confirmed by the XRD pattern. Compared with the traditional DSSCs without this compact layer, the solar energy-to-electricity conversion efficiency, short-circuit current and open-circuit potential of the DSSCs with the compact layer were improved by 33.3%, 20.3%, and 10.2%, respectively. This can be attributed to the merits brought by the compact layer. It can effectively improve adherence of TiO₂ to FTO surface, provide a larger TiO₂/FTO contact area, and reduce the electron recombination by blocking the direct contact between the redox electrolyte and the conductive FTO surface.     

Partially dyed-TiO2 dispersions for adaptation to the continuous fabrication of photoanodes

A new fabrication method of photoanodes for dye-sensitized solar cells (DSCs) is proposed using partially N3-dyed-TiO₂ nanoparticle dispersions. The photoanode fabrication method presented here is contrasted with a conventional low-temperature compression process, in that a time-consuming dye-adsorption step can be omitted, making DSCs more adaptable to a continuous printing process. The effects of the amount of dye-loadings, the degree of compression, and the film thickness on photovoltaic performances were examined. All processes were conducted at room temperature. The optimized film composed of partially dyed-TiO₂ led to sufficient interparticle connections to reach a power conversion efficiency of 5.0% under 100 mW cm⁻² AM1.5 illumination.     

Role of surface state on the electron flow in modified TiO2 film incorporating carbon powder for a dye-sensitized solar cell

An investigation of surface-related traps in nanostructured TiO₂ films modified by the incorporation of carbon powder was conducted by the potential-step chronoamperometric method. For the modification of the morphology and surface state of the nanoporous TiO₂ electrode, the incorporation of carbon into the white TiO₂ powder was accomplished. In the chronoamperometric data, all of the transients showed an initial fast phase (<1 s) followed by a slower phase which is related to the trap filling process. The trap-filling period of the carbon incorporated TiO₂ film becomes longer, as the applied negative potential increases, due to the widely distributed traps induced by the increased surface area. Furthermore, the film capacitance was derived as a function of the applied bias by integrating the current to time curves of the chronoamperometric data. The accumulated charge of the carbon incorporated TiO₂ film increases prominently in two regions. The dominant increase shown in the positive region (−0.7 to −0.9 V vs. Ag/AgCl at pH 13) of the flat band potential implies that the electron occupancy in the surface-related traps is increased. At a more negative potential (below −1.2 V vs. Ag/AgCl), electrons from the conduction band of the TiO₂ film substantially influence the total current, thereby inducing an exponential increase in the current. Therefore, it is found that most of the traps are located in the positive region of the flat band potential, since the Fermi level of the nanostructured TiO₂ film is positioned at −1.14 V vs. Ag/AgCl at pH 13. The trap sites in the sub-bandgap region of the TiO₂ film are important in the electron transport of photoinjected electrons from dye molecules and partially charge recombination with redox electrolyte in operating dye-sensitized solar cell. The influence of charge trap formed by increased surface states on the electron transport and electron transfer was investigated by photovoltage and photocurrent transient measurements.     

The improvement of electron transport rate of TiO2 dye-sensitized solar cells using mixed nanostructures with different phase compositions

Dye-sensitized solar cells (DSCCs) in the form of mixed nanostructures containing TiO₂ nanoparticles and nanowires with different weight ratios and phase compositions are reported. X-ray diffraction and field emission scanning electron microscopy analyses revealed that the synthesized TiO₂ nanoparticles had average crystallite size in the range 21–39 nm, whereas TiO₂ nanowires showed diameter in the range 20–50 nm. The indirect optical band gap energy of TiO₂ nanowires, anatase- and rutile-TiO₂ nanoparticles was calculated to be 3.35, 3.28 and 3.17 eV, respectively. The power conversion efficiency of the solar cells changed with nanowire to nanoparticle weight ratio, reaching a maximum at a specific value. An increase of 4.3% in cell efficiency was achieved by introducing 10 wt% nanowire into the as-synthesized TiO₂ nanoparticles (WP1 cell). Furthermore, an increase of 27.6% in cell efficiency was achieved by using crystalline anatase-TiO₂ nanoparticles rather than as-synthesized TiO₂ nanoparticles in WP1 solar cell. It was found that the power conversion efficiency and short circuit current of WP1 cell were decreased down to around 30.8% and 39.1%, respectively using rutile nanoparticles rather than anatase nanoparticles. The improvement of cell efficiency was related to rapid electron transport and less recombination of photogenerated electrons, as confirmed by electrochemical impedance spectroscopy.