Photoelectrochemical properties of ruthenium dye-sensitized nanocrystalline SnO2:TiO2 solar cells

The photoelectrochemical properties of RuL₂(NCS)₂ dye-sensitized nanocrystalline SnO₂:TiO₂ coupled and composite solar cells are reported. The coupled (bilayer) system shows higher incident photon-to-current conversion efficiency (IPCE) value than the composite (mixture) system. A maximum IPCE value attained 82.4% at 530 nm wavelength in the coupled system with 3.5 μm-thick SnO₂ and 7 μm-thick TiO₂. The higher IPCE value in the coupled system is attributed to the promotion of the charge separation by fast electron transfer process in the SnO₂/TiO₂/RuL₂(NCS)₂ system with different energy levels, different conduction band edge energy positions.     

Doubled layered ITO/SnO2 conducting glass for substrate of dye-sensitized solar cells

The effects of indium tin oxide (ITO) and ITO/SnO₂ conducting substrates on photovoltaic properties of dye-sensitized solar cells (DSCs) using nanocrystalline TiO₂ were studied. The decrease in fill factor of the DSCs was correlated to the increase in resistance of conducting substrate. The heat stability of ITO conducting glass was improved by depositing SnO₂ on ITO layer. The efficiency of the cells using double layered ITO/SnO₂ substrate remarkably increased comparing with that of the cells using ITO substrates. It is worth mentioning that increasing in sintering time, which enhanced the electronic contact between substrate and TiO₂, also modified the cell performance of MP-TiO₂ cells. Our experimental finding suggests that 3000 Å ITO substrate, which was covered by 1000 Å SnO₂ layer, exhibited the best properties for the DSCs.     

Single- and double-layered mesoporous TiO2/P25 TiO2 electrode for dye-sensitized solar cell

Nanocrystalline mesoporous titania (MP-TiO₂) was synthesized by surfactant-assisted templating method using tetraisopropyl orthotitanate modified with acetylacetone and laurylamine hydrochloride as template. The short-circuit photocurrent density (J_sc) of the cell made from MP-TiO₂ was much higher than that of the cell made from commercial P25 titania. The incident photon to current conversion efficiency (IPCE) spectra of thin MP-TiO₂ cell were higher than that of thick P25 cell in the region between 400 and 475 nm but lower than that of thick P25 cell in the red region, because the thickness of thin transparent MP-TiO₂ film was not enough to scatter the light leading to low absorbed spectra in red region. IPCE spectra of MP-TiO₂ can be improved by using the cell made from blended MP-TiO₂ with P25. The cell performance was improved with increasing sintering temperature. Double-layered titania cells were also fabricated to further improve the cell performance by increasing light scattering and amount of adsorbed dye. The solar energy conversion efficiency (η) up to 8.1% was obtained by using the double-layered titania cell sintered at 450 °C for 2 h.     

A 4.2% efficient flexible dye-sensitized TiO2 solar cells using stainless steel substrate

An efficient flexible dye-sensitized solar cells (DSSCs) using stainless steel supporting substrate for fabricating nanocrystalline TiO₂ film electrodes were developed, intending to improve the photoelectrochemical properties of plastic substrate-based DSSCs. The most important advantage of a stainless steel-based TiO₂ film electrode over a plastic-based electrode lies in its high-temperature sinterability. Optimal photovoltaic properties were obtained with a cell where the TiO₂ film was coated on both ITO- and SiO_x-sputtered stainless steel (denoted as TiO₂/ITO/SiO_x/StSt). The photocurrent of the flexible cells with a TiO₂/ITO/SiO_x/StSt electrode increased significantly, leading to a much higher overall solar conversion efficiency η of 4.2% at 100 mW/cm², based on short-circuit photocurrent density, open-circuit voltage and fill factor of 11.2 mA/cm², 0.61 and 0.61 V, respectively, than those reported for cells with plastic substrates.     

A novel UV-mediated low-temperature sintering of TiO2 for dye-sensitized solar cells

Titania pastes were fired at 450 °C in oxygen to give white titania that was used to prepare dye-sensitized solar cells (DSSC). Titania fired at lower temperature and/or under inert atmosphere have brown stripes and cells made from these stripes had no measurable efficiency. When the titania paste was screen printed and then heated and simultaneously irradiated with UV light, white stripes were obtained. Improved efficiency was noted for PV cells made from pastes heated at lower temperature under irradiation vs. cells made from low-temperature heated paste but without irradiation. UV irradiation appears to facilitate clean oxidation of residual organic materials in the titania precursor pastes. The best cells in our study made with our titania paste treated at 450 °C in oxygen had the following characteristics: efficiency=3.45%; V_oc=630 mV; J_sc=8.5 mA/cm²; and a fill factor=0.64.     

Down-converting lanthanide doped TiO2 photoelectrodes for efficiency enhancement of dye-sensitized solar cells

Lanthanide (Ln³⁺) doped TiO₂ down-conversion photoelectrodes (Ln³⁺ = Eu³⁺ and Sm³⁺ ions) are used to enhance the photovoltaic efficiency of dye-sensitized solar cells (DSSC). We report on achieving fill factors of 0.67 and 0.69 and efficiencies of 5.81% and 5.16% for Sm³⁺ and Eu³⁺, respectively. This is compared to the 4.23% efficiency for the undoped-titania photoelectrodes. This enhancement is probably due to the improved UV radiation harvesting via a down-conversion luminescence process by the lanthanide ions. The structure, optical and photoluminescence properties of the down-converting photoelectrode are characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive X-ray (EDX) and room temperature photoluminescence excitation and emission spectrofluorimetric measurements.     

Single-step fabrication of phase-controllable nanocrystalline TiO2 films for enhanced photoelectrochemical water splitting and dye-sensitized solar cells

We introduce a single-step procedure for growing a phase-controllable bilayer-structured TiO₂ film directly onto transparent conductive oxide glass by precipitation from hydrolysis of TiCl₄ in acid solution containing sulfate ions. The obtained bilayer-structured film with anatase nanoparticles in the inner layer which provide high surface area, and an outer layer of larger rutile particles for incident light scattering. In both the water splitting and the dye-sensitized solar cells under AM 1.5 simulated solar light, the bilayer-structured film outperformed the single layer-structured films with either anatase or rutile TiO₂ alone by at least 50%.     

Nanostructured photoelectrode consisting of TiO2 hollow spheres for non-volatile electrolyte-based dye-sensitized solar cells

A photoelectrode consisting of titania hollow spheres for dye-sensitized solar cells (DSSCs) is prepared by a paste method and the effect of the nanostructure on the performance of DSSCs with non-volatile electrolytes is investigated. The structure of the hollow sphere (HS) electrode with a large pore size and a high porosity allows highly viscous non-volatile electrolytes to penetrate the electrode thoroughly. Furthermore, its outstanding light-harvesting efficiency and long electron diffusion length make the efficiency of the DSSCs with the HS electrode comparable with those of a conventional nanocrystalline electrode, in spite of the smaller amount of the adsorbed dye, when oligomer electrolytes are used. The results show that the structure of a photoelectrode highly improves the performance of the device and the HS electrode is an effective structure for the use of non-volatile electrolytes in DSSCs.     

Stability of the SnO2/MgO dye-sensitized photoelectrochemical solar cell

Dye-sensitized solar cells made of TiO₂ are extensively studied as a cheap alternative to conventional photovoltaic cells. The other familiar stable oxide material of similar band gap suitable for dye sensitization is SnO₂. Although cells based only of SnO₂ are prone to severe recombination losses, the cells made of SnO₂/MgO films where the SnO₂ crystallite is surface covered with an ultra-thin shell of MgO, deliver reasonably high efficiencies. It is found that SnO₂/MgO cells resist dye and electrolyte degradation better than TiO₂ cells. Furthermore, the ultra-thin barrier of MgO on SnO₂ remains intact during prolonged usage or storage of the cell.     

Increase in photovoltaic performances of dye-sensitized solar cells—Modification of interface between TiO2 nano-porous layers and F-doped SnO2 layers

In order to improve the physical and chemical contacts between a porous TiO₂ layer and an F-doped SnO₂ transparent conductive layer (FTO), the surface of the FTO layer is polished. After polishing, the surface roughness decreased. However, light transmittance and sheet resistance did not vary largely. The short circuit current (J_sc) and efficiencies increased after the FTO was polished. It was found that the interfacial charge transfer between a TiO₂ layer and an FTO layer decreased by impedance measurement, which suggests that contacts between an FTO and a TiO₂ layer are improved because of the flatted surfaces or removal of electrical impurities. We propose one of the industrially important phenomena that surface polishing of FTO is one of the ways to increase photovoltaic performances for DSCs.     

Unique TiO2 paste for high efficiency dye-sensitized solar cells

A novel titanium oxide paste based on Pechini sol-gel method and nanocrystalline titanium oxide powder have been successfully developed. Titanium oxide layers possess high inner surface area assuring high dye loading and well-connected nanocrystalline grains assuring good electron transport within the layer. The dye-sensitized layers have been used to assemble dye-sensitized solar cells with acetonitrile- and ionic liquid-based electrolyte. Overall conversion efficiencies of dye-sensitized solar cells (DSSCs) determined under standard test conditions (100 mW/cm², 25 °C and AM 1.5 G) are 10.2% for acetonitrile and 7.3% for ionic liquid-based electrolyte.     

ITO/ATO/TiO2 triple-layered transparent conducting substrates for dye-sensitized solar cells

A novel transparent conductive oxide film based on the triple-layered indium tin oxide (ITO)/antimony-doped tin oxide (ATO)/titanium oxide (TiO₂) has been developed for dye-sensitized solar cells by using radio frequency magnetron sputtering technique. Effects of the absence and presence of TiO₂ layer and the ITO layer thickness were investigated. Deposition of ATO layer was found to stabilize the thermal instability of ITO. Little change in sheet resistance and optical transmittance was observed by introduction of insulating thin TiO₂ layer on top of the ATO layer, whereas photovoltaic performance was significantly influenced. The conversion efficiency was improved from 4.57% without TiO₂ layer to 6.29% with TiO₂ layer. The enhanced photovoltaic performance with addition of TiO₂ layer was attributed mainly to the improved adhesion and partially to the reduced electron loss at the ITO/ATO conductive layer. Increase in the ITO layer thickness resulted in a slight decrease in photocurrent due to the reduced optical transmittance. When compared with the conventional fluorine-doped tin oxide (FTO), the ITO/ATO/TiO₂ conductive material exhibited similar photocurrent density but higher photovoltage and fill factor, resulting in better conversion efficiency.     

Columnar rutile TiO2 based dye-sensitized solar cells by radio-frequency magnetron sputtering

Columnar-structured rutile TiO₂ film with a thickness of 1.4 μm is prepared using the radio-frequency (RF) magnetron sputtering technique, for application in dye-sensitized solar cells (DSSCs). Pure rutile TiO₂ films are fabricated by controlling the substrate temperature during sputtering and using a substrate with a rough surface morphology. Successive substrate heating to 623 K induces the growth of a rutile TiO₂ film that has a specific direction in the (1 1 0) plane, which results in a decrease in the average grain size. This causes in an increase of dye uptake and thereby contributes to enhancement of the photocurrent in the DSSC.     

Electrodeposition of TiO2/SiO2 nanocomposite for dye-sensitized solar cell

For the working electrode of dye-sensitized solar cell (DSC), TiO₂/SiO₂ nanocomposite materials were electrodeposited on transparent fluorine doped tin oxide-coated glass by cathodic electrodeposition at room temperature. The electrode and DSC fabricated with TiO₂/SiO₂ nanocomposite were characterized with photocurrent density, X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM) and a photovoltaic performance test. On the electrodeposition, the addition of an appropriate amount of SiO₂ in the bath containing TiO₂ slurry was essential to achieve the superior crystallinity, photocurrent density and photovoltaic performance of the resulting TiO₂/SiO₂ electrode, which was significantly superior to a bare TiO₂ electrode. This enhanced performance of optimized TiO₂/SiO₂ electrode was ascribed to the role of SiO₂ as an energy barrier, increasing the physical separation of injected electrons and oxidized dyes/redox couple, and thereby retarding the recombination reactions in the resulting DSC.     

Fabrication of solid-state dye-sensitized TiO2 solar cells combined with polypyrrole

A solid-state solar cell was fabricated by photoelectrochemical polymerization of pyrrole on porous nanocrystalline TiO₂ electrode sensitized by the Grätzel dye, cis-di(thiocyanato)-N,N′-bis(2,2′-bipyridyl-4,4′-dicarboxylic acid)-ruthenium (II) dihydrate, [RuL₂(NCS)₂]), or a newly synthesized cis-Ru(dcb)₂(pmp)₂ (pmp=3-(pyrrole-1-ylmethyl)-pyridine). Polypyrrole successfully worked as a hole-transport layer with improvement of the cell characteristics when the TiO₂ cell with cis-Ru(dcb)₂(pmp)₂ was compared with the similarly fabricated cells using [RuL₂(NCS)₂]. The improvement by using Ru(dcb)₂(pmp)₂ can be explained as due to direct molecular wiring of the polymer-chain to the excited metal center of the complex.     

Effects of silver particles on the photovoltaic properties of dye-sensitized TiO2 thin films

To evaluate the possibility of using the plasmon resonance effect to enhance the efficiency of photochemical cells, cis-(SCN)₂Bis(2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium (II) dye-sensitized cells were used to measure the photoresponse of TiO₂ film electrodes before and after deposition of Ag particles. The deposited Ag particles created a film with Ag islands. We found that the photoresponse in the visible region increased as the mass-equivalent Ag-island film thickness, t_Ag, increased to 3.3 nm, but decreased when t_Ag was further increased to 6 nm. On the other hand, compared with bare TiO₂ films, the photoresponse in the UV region decreased for any level of Ag islands. These results suggest that under proper conditions, enhancement of the optical absorption of the dye by the Ag plasmon resonance effect contributes to the photocurrent, and indicates the possibility of improving the energy conversion efficiency of photoelectrochemical cells with Ag-island films.     

Preparation of TiO2 nanocrystalline electrode for dye-sensitized solar cells by 28 GHz microwave irradiation

Microwave preparation of TiO₂ nanocrystalline electrode for use in dye-sensitized solar cells is examined. A multi-mode microwave heating system operating at a frequency of 28 GHz is used to produce rapid processing. Well-sintered TiO₂ nanocrystalline thin film is successfully fabricated on transparent conductive FTO glass electrode. Photoelectron energy conversion efficiency of 5.51% is achieved in an electrode prepared by 28 GHz microwave irradiation at 0.7 kW for 5 min.     

Light harvesting enhancement for dye-sensitized solar cells by novel anode containing cauliflower-like TiO2 spheres

Cauliflower-like TiO₂ rough spheres, which are about 200 nm large, have greatly enhanced light harvesting efficiency and energy conversion efficiency of dye-sensitized solar cells (DSC), due to their high light scattering effect and large BET surface area (80.7 m² g⁻¹) even after calcinations at 450 °C for 30 min. The large size TiO₂ rough and smooth spheres, produced at different initial temperatures by hydrolysis of Ti(OBu)₄ with P105 (EO₃₇PO₅₆EO₃₇) or F68 (EO₇₈PO₃₀EO₇₈) tri-block copolymer as structural agents, have nearly the same diameter of ∼275 nm and strong light scattering effects in the wavelength of 400–750 nm. However, rough spheres have even higher light scattering effect and larger BET surface area than smooth spheres for the roughness of the surface. By adding 25 wt.% large TiO₂ spheres into the over-layer of TiO₂ film composed of ∼20 nm TiO₂ particles as light scattering centers, the energy conversion efficiency of the film containing rough spheres reaches 7.36%, much larger than that of smooth spheres (6.25%). From another point of view, the TiO₂ rough spheres may have the satisfying ability in other fields of application such as photo-catalysis, drug carriers and so on.     

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.     

Theoretical modeling of TiO2/TCO interfacial effect on dye-sensitized solar cell performance

A theoretical model based on an integration of both Schottky barrier model and electron diffusion differential model was developed to determine the TiO₂/TCO interfacial effect on the current–voltage (J–V) characteristics of a dye-sensitized solar cell (DSSC). The thermionic-emission theory was appropriately applied to describe the electron transfer at the TiO₂/TCO interface. A parametric analysis was conducted to study how the photoelectric outputs varied with multiple independent variables, such as Schottky barrier height (φ_b) and temperature. It was found that the variation of the maximum DSSC power output (P_max) was insignificant when φ_b varied at a low value; however, an increase in φ_b exceeding a critical value caused an apparent decrease in the maximum DSSC power output. The theoretical results were quantitatively compared and agreed very well with published theoretical results. The experimental data from literature were found to agree well with the present theoretical results, qualitatively validating the present model. The theoretical model can be applied to facilitate selection of suitable TCO material in DSSC design to avoid the adverse TiO₂/TCO interfacial effect.