Nanocrystalline titanium dioxide sensitised with natural dyes for eco-friendly solar cell application

Indigenously available natural dyes have been used as natural sensitisers for dye-sensitised solar cells (DSSCs) in this study. The chlorophyll extract from Azadirachta indica (Neem) leaves and anthocyanin extract from poinsettia bracts were obtained using ethanol. Nanoparticles of TiO₂ having an average size of 80 nm were deposited on fluorine-doped tin oxide (FTO) coated glass using the electrophoretic deposition method. Counter electrode was prepared by spraying conductive graphite over FTO glass substrates. A sandwich-type cell was assembled, and the fill factor and the power conversion efficiency were measured under a light source simulating AM 1.5 with an intensity of 100 mW/cm². DSSCs containing chlorophyll and anthocyanin exhibited open circuit voltages of 404 and 406 mV with fill factors of 40.1% and 45.8%, respectively. The mixture of the two natural dyes as sensitiser for DSSCs gave the best photovoltaic conversion efficiency of approximately 1%.     

Probing mechanism of dye double layer formation from dye-cocktail solution for dye-sensitized solar cells

Absorption of photon in wide wavelength region is an important requirement for the enhancement of photoconversion efficiency of dye-sensitized solar cells (DSSC). Lack of photon absorption from visible to NIR wavelength region by a single dye requires the use of plural dyes for the panchromatic sensitization of nanoporous TiO₂. To our incredible surprise, when a dye cocktail of organic dye NK3705 and inorganic ruthenium based dye Z907 was implied for the dye adsorption, it led to the formation of dye double layer in spite of random arrangement of two dyes as evidenced from confocal laser microscopic investigations. Investigation pertaining to the evaluation of rate of dye adsorption and dye desorption for different organic and inorganic sensitizing dyes suggests that a combination of one dye with faster diffusion along with weak binding on TiO₂ surface and another dye with slow diffusion along with strong binding leads to the formation of dye double layer from a dye mixture by a simple dipping process.     

The optical properties of nanoporous structured titanium dioxide and the photovoltaic efficiency on DSSC

This study examined the characterization of nanoporous structured titanium dioxide and its application to dye-sensitized solar cells (DSSCs). TEM revealed nanopore sizes of 10.0 nm with a regular hexagonal form. When nanoporous structured TiO₂ was applied to DSSC, the energy conversion efficiency was enhanced considerably compared with that using nanometer sized TiO₂ prepared using a hydrothermal method. The energy conversion efficiency of the DSSC prepared from nanoporous structured TiO₂ was approximately 8.71% with the N719 dye under 100 mW cm⁻² simulated light. FT-IR spectroscopy showed that the dye molecules were attached perfectly to the surface and more dye molecules were absorbed on the nanoporous structured TiO₂ than on the nano-sized TiO₂ particles prepared using a conventional hydrothermal method. Electrostatic force microscopy (EFM) showed that the electrons were transferred rapidly to the surface of the nanoporous structured TiO₂ film.     

The effects of the thickness of TiO2 films on the performance of dye-sensitized solar cells

Nanocrystalline anatase TiO₂ thin films with different thicknesses (0.5-2.0 μm) have been deposited on ITO-coated glass substrates by a sol-gel method and rapid thermal annealing for application as the work electrode for dye-sensitized solar cells (DSSC). From the results, the increases in thickness of TiO₂ films can increase adsorption of the N3 dye through TiO₂ layers to improve the short-circuit photocurrent (J_sc) and open-circuit voltage (V_oc), respectively. However, the J_sc and V_oc of DSSC with a TiO₂ film thickness of 2.0 μm (8.5 mA/cm² and 0.61 V) are smaller than those of DSSC with a TiO₂ film thickness of 1.5 μm (9.2 mA/cm² and 0.62 V). It could be due to the fact that the increased thickness of TiO₂ thin films also resulted in a decrease in the transmittance of TiO₂ thin films thus reducing the incident light intensity on the N3 dye. An optimum power conversion efficiency (η) of 2.9% was obtained in a DSSC with the TiO₂ film thickness of 1.5 μm.     

Charge recombination reduction in dye-sensitized solar cells by depositing ultrapure TiO2 nanoparticles on “inert” BaTiO3 films

Ultrapure TiO₂ nanoparticles (∼5 nm in size) were supported on “inert” BaTiO₃ films by TiCl₄ treatment, which was used to fabricate dye-sensitized solar cells (DSSCs). The optimized electrode, designated as BaTiO₃/TiO₂(4), was obtained upon four cycles of TiCl₄ treatment. DSSC with BaTiO₃/TiO₂(4) electrode exhibits superior power conversion efficiency (PCE) compared to that with conventional anatase TiO₂ (∼25 nm in size) electrode. The interfacial charge recombination kinetics was investigated by electrochemical impedance spectroscopy (EIS) and intensity-modulated photocurrent/photovoltage spectroscopy (IMPS/IMVS). In contrast to DSSC with anatase TiO₂ electrode, the dramatically enhanced electron lifetime for DSSC with BaTiO₃/TiO₂(4) electrode could be attributed to the decrease of recombination reaction at the TiO₂ photoelectrode/electrolyte interface. It is proposed that the lower interfacial charge recombination can be related to the relatively shallower trap distributions in DSSC with BaTiO₃/TiO₂(4) electrode.     

Improving conversion efficiency of dye-sensitized solar cells by metal plasma ion implantation of ruthenium ions

Dye-sensitized solar cells (DSSC) are based on the concept of photosensitization of wide-band-gap mesoporous oxide semiconductors. At present, DSSC have ventured into advanced development and pilot production. Our current research emphasizes on improvements on titanium dioxide (TiO₂) photosensitivity under visible light irradiation by using metal plasma ion implantation (MPII). The anatase TiO₂ electrode was prepared via a sol-gel process and deposited onto indium-tin oxide glass substrates. Subsequently, the as-deposited TiO₂ films were subjected to MPII at 20 keV in order to incorporate ruthenium (Ru) atoms onto the TiO₂ surface layer. The Ru-implanted TiO₂ thin film possessed nanocrystalline Ru clusters of 20 nm in diameter and distributed in near surface layer of TiO₂ films. The Ru clusters showed effective in both prohibiting electron-hole recombination and generating additional Ru-O impurity levels for the TiO₂ band gap structure. A significant reduction of TiO₂ band gap energy from 3.22 to 3.11 eV was achieved, which resulted in the extension of photocatalysis of TiO₂ from UV to Vis regime. A small drop of photoelectric performance of 8% was obtained due to the incorporation of Ru atoms in the surface layer of TiO₂, a similar side effect as observed in the Fe-implanted TiO₂. However, the overall retention of the photocatalysis capability is as high as 92% when switch from UV to Vis irradiation. The improvement of the photosensitivity of TiO₂ DSSC by means of metal plasma ion implantation is promising.     

Fabrication of dye-sensitized solar cells using TiO2-nanotube arrays on Ti-grid substrates

Self-aligned TiO₂ nanotube arrays (20 μm in length) were fabricated by anodic oxidation of Ti-grid with a thickness of 100 μm in an ethylene glycol electrolyte with an addition of H₂O (1.5 vol.%) and NH₄F (0.2 wt.%). Voltage applied between Ti and Pt cathodes is 60 V at ~ 22 °C. Dye-sensitized solar cell utilizing photoanode structure of TiO₂-nanotube/Ti-grid was fabricated with no transparent conducting oxide (TCO) layer, in which Ti-grid replaces TCO. Overall photoconversion efficiency is very low (< 0.5%) due to the large pore size (100 nm in diameter) of the nanotubes, which may cause insufficient dye molecules to be attached, thus limiting light harvesting.     

Iron promotion of the TiO2 photosensitization process towards the photocatalytic oxidation of azo dyes under solar-simulated light irradiation

The photocatalytic oxidation of the azo dye Orange-II (Or-II) using Fe loaded TiO₂ (Fe–TiO₂) was studied under ultraviolet (UV), visible (vis) and simultaneous UV–vis irradiations using a solar light simulator. Photocatalysts were characterized by means of XRD, SEM-EDX, FTIR and DRS. Fe³⁺ species, identified in XPS analyses, were responsible of the increased absorption of visible light. Moreover, DRS analyses showed a decrease in the bandgap due to Fe³⁺ loading. Photocatalystic tests proved that Fe modification enhanced the TiO₂ photocatalytic activity towards Or-II photodegradation under simultaneous UV–vis irradiation. Even so, the performance of the Fe–TiO₂ samples towards the photodegradation of phenol, under UV irradiation, was lower than TiO₂ suggesting the recombination of the UV photogenerated electron–hole pair. Therefore, results evidence a Fe³⁺ promotion of the electron caption in the photosensitization process of TiO₂ by Or-II acting as a sensitizer. Such process leads to the Or-II photooxidation under UV–vis irradiation by losing energy in electron transferring processes to sensitize TiO₂, and, the formation of reactive oxygen species promoted by the injected electron to the TiO₂ conduction band.     

Hybrid photovoltaic cells with II–VI quantum dot sensitizers fabricated by layer-by-layer deposition of water-soluble components

We present the fabrication of all solid state heterojunction photovoltaic devices consisting of TiO₂ films sensitized by colloidal CdSe and CdTe quantum dots (QDs) and a hole transport layer of the conjugated polymer poly(9,9-dioctyl-fluorene-co-N-(4-butylenphenyl)diphenylamine). The sensitized films were prepared by alternating the layer-by-layer deposition of TiO₂ nanoparticles, water-soluble semiconductor QDs and polycations. Photovoltaic devices sandwiched between fluorinated tin oxide and gold electrodes showed a high rectification ratio and photovoltages of up to 1.15 V. Effective sensitization was observed for CdSe QDs, while incorporated CdTe QDs apparently had no such effect. These findings are explained by confinement effects in QDs.     

Reactive dyes remotion by porous TiO2-chitosan materials

In this work, the aim was to evaluate the remotion (adsorption plus degradation) of two reactive dyes, Methylene Blue (MB) and Benzopurpurin (BP), from aqueous solutions by the utilization of TiO2-chitosan microporous materials. Two different TiO2-chitosan hybrid materials were synthesized: TiO2-Chit A with 280 mg chitosan/gTiO2 and TiO2-Chit B with 46.76 mg chitosan/g TiO2. Adsorption data obtained at different solution temperatures (25, 35, and 45 degrees C) revealed an irreversible adsorption that decrease with the increment of T. Langmuir, Freundlich and Sips isotherm equation were applied to the experimental data. The obtained parameters and correlation coefficient showed that the adsorption of both dyes on TiO2-Chit A at the three work temperatures was best predicted by the Langmuir isotherm, while Sips equation adjusted better to adsorption data on TiO2-Chit B. The adsorption enthalpy was relatively high and varied with T, indicating that interaction between adsorbent and adsorbate molecules was not only physical but chemical. There is a change in the adsorption heat capacity, (Delta(ads)C(p)<0), related with intense hydrophobic interactions. The kinetic adsorption data were processed by the application of Lagergren and Avrami models. It was found that adsorption of both dyes on both adsorbents under the operating conditions was best predicted by Avrami model. The variation of kinetic order, n, and k(av) with T are related to a pore followed by intra particle diffusion control of the adsorption rate. MB photodegradation on both TiO2-chitosan hybrid materials was of 91 (in A) and 41% (in B) and augmented with the chitosan content. For BP can be seen that the process in darkness resulted in a high remotion capacity than in UV light presence.     

Photocatalytic degradation of dyes and organic contaminants in water using nanocrystalline anatase and rutile TiO2

Nanocrystalline TiO₂ was synthesized by controlled hydrolysis of titanium tetraisopropoxide. The anatase phase was converted to rutile phase by thermal treatment at 1023 K for 11 h. The catalysts were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), Fourier-transform infrared absorption spectrophotometry (FT-IR) and N₂ adsorption (BET) at 77 K. This study compare the photocatalytic activity of the anatase and rutile phases of nanocrystalline TiO₂ for the degradation of acetophenone, nitrobenzene, methylene blue and malachite green present in aqueous solutions. The initial rate of degradation was calculated to compare the photocatalytic activity of anatase and rutile nanocrystalline TiO₂ for the degradation of different substances under ultraviolet light irradiation. The higher photocatalytic activity was obtained in anatase phase TiO₂ for the degradation of all substances as compared with rutile phase. It is concluded that the higher photocatalytic activity in anatase TiO₂ is due to parameters like band-gap, number of hydroxyl groups, surface area and porosity of the catalyst.     

Photocatalytic degradation of dyes and organic contaminants in water using nanocrystalline anatase and rutile TiO2

Nanocrystalline TiO₂ was synthesized by controlled hydrolysis of titanium tetraisopropoxide. The anatase phase was converted to rutile phase by thermal treatment at 1023 K for 11 h. The catalysts were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), Fourier-transform infrared absorption spectrophotometry (FT-IR) and N₂ adsorption (BET) at 77 K. This study compare the photocatalytic activity of the anatase and rutile phases of nanocrystalline TiO₂ for the degradation of acetophenone, nitrobenzene, methylene blue and malachite green present in aqueous solutions. The initial rate of degradation was calculated to compare the photocatalytic activity of anatase and rutile nanocrystalline TiO₂ for the degradation of different substances under ultraviolet light irradiation. The higher photocatalytic activity was obtained in anatase phase TiO₂ for the degradation of all substances as compared with rutile phase. It is concluded that the higher photocatalytic activity in anatase TiO₂ is due to parameters like band-gap, number of hydroxyl groups, surface area and porosity of the catalyst.     

Sputter deposition and surface treatment of TiO2 films for dye-sensitized solar cells using reactive RF plasma

Sputter deposition followed by surface treatment was studied using reactive RF plasma as a method for preparing titanium oxide (TiO₂) films on indium tin oxide (ITO) coated glass substrate for dye-sensitized solar cells (DSCs). Anatase structure TiO₂ films deposited by reactive RF magnetron sputtering under the conditions of Ar/O₂(5%) mixtures, RF power of 600 W and substrate temperature of 400 °C were surface-treated by inductive coupled plasma (ICP) with Ar/O₂ mixtures at substrate temperature of 400 °C, and thus the films were applied to the DSCs. The TiO₂ films made on these experimental bases exhibited the BET specific surface area of 95 m²/g, the pore volume of 0.3 cm²/g and the TEM particle size of ∼ 25 nm. The DSCs made of this TiO₂ material exhibited an energy conversion efficiency of about 2.25% at 100 mW/cm² light intensity.     

Polymer solar cells with a TiO2:Ag layer

Photovoltaic (PV) polymer solar cells with Ag and titanium dioxide were fabricated to improve the PV performance by increasing the amount of Ag in TiO₂ (by 3, 5, 7, and 10%). Sol–gel method was used to obtain amorphous or crystalline form of titanium dioxide layers. The solar cells with poly(3-hexylthiophene) and [6,6]-phenyl-C61-butyric acid methyl ester active layer in two various positions of titanium dioxide in device were tested. Higher PV performance was received by introducing TiO₂ with 5% of Ag between ITO and PEDOT:PSS in device and by heating the layer at 130 °C. The viscosity of applied PEDOT:PSS strongly influences the values of power conversion efficiency of the constructed polymer devices with titanium dioxide.     

Photocatalytic degradation of Azure and Sudan dyes using nano TiO2

The present study investigates the dependence of photocatalytic rate on molecular structure of the substrate that is degraded. The photocatalytic degradation of Azure (A and B) and Sudan (III and IV) dyes, having similar structure, but different functional groups, were investigated with two catalysts. The photocatalytic activity of solution combustion synthesized TiO(2) (CS TiO(2)) was compared with that of Degussa P-25 for degrading these dyes. The effect of solvents and mixed-solvent system on photodegradation of Sudan III was investigated. The photodegradation rate was found to be higher in solvents with higher polarity. The effect of pH and the presence of metal ions in the form of chloride and nitrate salt, on degradation rate of Azure A was also investigated. The metal ions significantly reduced the photocatalysis rates. A detailed Langmuir-Hinshelwood kinetic model has been developed to explain the effect of metal ions on degradation rate of the substrate. This model elucidates the contribution of holes and electrons towards degradation of the dye.     

Fabrication and properties of meso-macroporous electrodes screen-printed from mesoporous titania nanoparticles for dye-sensitized solar cells

A meso-macroporous TiO₂ film electrode was fabricated by using mesoporous TiO₂ (m-TiO₂) nanoparticles through a screen-printing technique in order to efficiently control the main fabrication step of dye-sensitized solar cells (DSSCs). The qualities of the screen-printed m-TiO₂ films were characterized by means of spectroscopy, electron microscopy, nitrogen adsorption–desorption and photoelectrochemical measurements. Under the optimal paste composition and printing conditions, the DSSC based on the meso-macroporous m-TiO₂ film electrode exhibits an energy conversion efficiency of 4.14%, which is improved by 1.70% in comparison with DSSC made with commercially available nonporous TiO₂ nanoparticles (P25, Degussa) electrode printed with a similar paste composition. The meso-macroporous structure within the m-TiO₂ film is of great benefit to the dye adsorption, light absorption and the electrolyte transportation, and then to the improvement of the overall energy conversion efficiency of DSSC.     

Influence of gas flow during vacuum cold spraying of nano-porous TiO2 film by using strengthened nanostructured powder on performance of dye-sensitized solar cell

Nano-porous TiO₂ films, which can be applied to the flexible dye-sensitized solar cell (DSC), were deposited by vacuum cold spraying at room temperature with the strengthened nanostructured TiO₂ powder as feedstock. The spraying was conducted under different accelerating gas flows resulting in various particle velocities. Results show that the short-circuit photocurrent density of the cell (N719 dye) increases from 8.3 to 9.8 mA/cm² with the increase in gas flow from 3 to 7.5 L/min. A maximum overall energy conversion efficiency of 4.2% was obtained for the DSC with the TiO₂ film deposited at the gas flow of 7.5 L/min. The influence of particle velocity on the electron transport parameters and cell performance was discussed to reveal the important role of particle velocity in the formation of particle connection through high impact pressure during vacuum cold spraying.     

Determination of photo-catalytic activity of un-doped and Mn-doped TiO2 anatase powders on acetaldehyde under UV and visible light

Titanium dioxide (TiO₂) photocatalytic powder materials doped with various levels of manganese (Mn) were synthesized to be used as additives to wall painting in combating indoor and outdoor air pollution. The heterogeneous photocatalytic degradation of gaseous acetaldehyde (CH₃CHO) on Mn-TiO₂ surfaces under ultraviolet and visible (UV/Vis) irradiation was investigated, by employing the Photochemical Static Reactor coupled with Fourier-Transformed Infrared spectroscopy (PSR/FTIR) technique. Experiments were performed by exposing acetaldehyde (~ 400 Pa) and synthetic air mixtures (~ 1.01 × 10⁵ Pa total pressure) on un-doped TiO₂ and doped with various levels of Mn (0.1-33% mole percentage) under UV and visible irradiation at room temperature. Photoactivation was initiated using either UV or visible light sources with known emission spectra. Initially, the photo-activity of CH₃CHO under the above light sources, and the physical adsorption of CH₃CHO on Mn-TiO₂ samples in the absence of light were determined prior to the photocatalytic experiments. The photocatalytic loss of CH₃CHO on un-doped TiO₂ and Mn-TiO₂ samples in the absence and presence of UV or visible irradiation was measured over a long time period (≈ 60 min), to evaluate their relative photocatalytic activity. The gaseous photocatalytic end products were also determined using absorption FTIR spectroscopy. Carbon dioxide (CO₂) was identified as the main photocatalysis product. It was found that 0.1% Mn-TiO₂ samples resulted in the highest photocatalytic loss of CH₃CHO under visible irradiation. This efficiency was drastically diminished at higher levels of Mn doping (1-33%). The CO₂ yields were the highest for 0.1% Mn-TiO₂ samples under UV irradiation, in agreement with the observed highest CH₃CHO decomposition rates. It was demonstrated that low-level (0.1%) doping of TiO₂ with Mn results in a significant increase of their photocatalytic activity in the visible range, compared to un-doped TiO₂. This elevated activity is lost at high doping levels (1-33%). Finally, the photocatalytic degradation mechanism of CH₃CHO on 0.1% Mn-TiO₂ surfaces under visible irradiation leading to low CO₂ yields is different than that under UV irradiation resulting to high CO₂ yields.     

A novel lanthanum hydroxide nanostructure prepared by cathodic electrodeposition

A novel and interesting nanostructure of La(OH)₃ was prepared by electrochemical method under mild conditions without any hard templates and surfactants. In this method, La(OH)₃ was galvanostatically deposited from low-temperature nitrate bath on the steel substrate by electrogeneration of base. X-ray results showed that the obtained deposit has single crystalline hexagonal phase of La(OH)₃. Morphological characterization revealed that the product has compact morphology with capsule-like structures having approximately an average diameter of 15 nm and the length of up to 50 nm. The results showed that low-temperature cathodic electrodeposition can be recognized as an easy and facile method for the synthesis of La(OH)₃ nanocapsules.     

Optimization of the cutting process of multi-wall carbon nanotubes for enhanced dye-sensitized solar cells

Dye-sensitized solar cells (DSSCs) were fabricated based on multi-wall carbon nanotube (MWCNT)-TiO₂ photo-anodes, which were prepared by the procedures of cutting MWCNTs and subsequent immobilization TiO₂ on MWCNTs. Through a detailed study, we found that cut-MWCNTs with proper ultrasonication time (2 h) and proper content (0.075%) resulted in 58 and 40% increase in short-circuit photocurrent and overall energy conversion efficiency, respectively, compared with that of a DSSC using only TiO₂ photo-anode. The enhancement of cut-MWCNTs for DSSC was attributed to the introduction of percolative conductive paths which facilitate the rapid electron transfer.