Optimization of the dye-sensitized solar cell performance by mechanical compression

In this study, the P25 titanium dioxide (TiO₂) nanoparticle (NP) thin film was coated on the fluorine-doped tin oxide (FTO) glass substrate by a doctor blade method. The film then compressed mechanically to be the photoanode of dye-sensitized solar cells (DSSCs). Various compression pressures on TiO₂ NP film were tested to optimize the performance of DSSCs. The mechanical compression reduces TiO₂ inter-particle distance improving the electron transport efficiency. The UV–vis spectrophotometer and electrochemical impedance spectroscopy (EIS) were employed to quantify the light-harvesting efficiency and the charge transport impedance at various interfaces in DSSC, respectively. The incident photon-to-current conversion efficiency was also monitored. The results show that when the DSSC fabricated by the TiO₂ NP thin film compressed at pressure of 279 kg/cm², the minimum resistance of 9.38 Ω at dye/TiO₂ NP/electrolyte interfaces, the maximum short-circuit photocurrent density of 15.11 mA/cm², and the photoelectric conversion efficiency of 5.94% were observed. Compared to the DSSC fabricated by the non-compression of TiO₂ NP thin film, the overall conversion efficiency is improved over 19.5%. The study proves that under suitable compression pressure the performance of DSSC can be optimized.     

Preparation of ZnO-coated TiO2 electrodes using dip coating and their applications in dye-sensitized solar cells

This study investigates the applicability of a ZnO-coated TiO₂ working electrode in a dye-sensitized solar cell (DSSC). This working electrode was designed and fabricated by the following procedures: (1) two consecutive TiCl₄ treatments were performed when preparing the TiO₂ electrode, one prior to and the other following the spin printing of the TiO₂ colloid on a FTO-glass (Fluorine doped tin oxide, SnO₂:F) substrate; (2) a simple dip coating method was used to fabricate a ZnO-coated TiO₂ electrode by immersing a FTO-glass substrate with a TiO₂ film in a solution of zinc acetate dehydrate [Zn(CH₃COO)₂?2H₂O] and ethanol. This working electrode was then immersed in a solution of N-719 (Ruthenium) dye at a temperature of 70 °C for a preset duration. Finally, the DSSC was assembled, and the short-circuit photocurrent, the open-circuit photovoltage, and the power conversion efficiency of DSSC were measured using an I–V measurement system. The effects of the concentration of Zn(CH₃COO)₂?2H₂O, the duration of dipping, and the dye loading on the power conversion efficiency of a DSSC were also examined. Most importantly, this study shows that the power conversion efficiency of the DSSC with a ZnO-coated TiO₂ electrode (6.62%) substantially exceeds that of the conventional DSSC with a TiO₂ electrode (5.45%) due to the effects of a ZnO barrier and the TiCl₄ treatment.     

Preparation of polyaniline/TiO2 nanocomposite film with good adhesion behavior for dye‐sensitized solar cell application

In this study, novel Polyaniline (PAni)/TiO₂ nanocomposites were applied on fluoride‐doped tin oxide (FTO) glass to act as an efficient counter electrode in dye‐sensitized solar cell (DSSC) application. PAni/TiO₂ nanocomposites were synthesized via chemical oxidation process using di‐2‐ethylhexylsulfosuccinate sodium salt (NaDEHS) as dopant. The nanocomposites were characterized using fourier transform infrared and ultraviolet‐visible spectrometers. In the application of PAni as the counter electrode in the solar cell, the film showed poor adhesion on the FTO glass. Palm oil‐based alkyd was introduced into the nanocomposite mixture to improve the adhesion of the film. The findings in the work show that strong adhesion of PAni on FTO glasses has led to higher incident photon to current conversion efficiency (IPCE) in solar cell. The short circuit current (Jsc), Voc (open circuit voltage), and IPCE of the resulted PAni/TiO₂ counter electrode with good adhesion in DSSC are 15.8 mA/cm², 670 mV, and 3.0%, respectively. POLYM. COMPOS., 34:1884–1891, 2013. © 2013 Society of Plastics Engineers     

Effects of Eu3+ and Er3+ Doping on Photoelectrical Performance of Dye‐Sensitized Solar Cells

A novel tri‐layer film photoelectrode structure of DSSC by introducing Eu³⁺ and Er³⁺ ions into TiO₂ film was proposed. The photoelectric conversion efficiency of the DSSC with Er³⁺:TiO₂/Eu³⁺:TiO₂/TiO₂ tri‐layer electrode reaches 7.41%, increased by a factor of 1.44 compared to that of the DSSC without Eu³⁺ and Er³⁺ doping. The higher efficiency for DSSC with the tri‐layer electrode is mainly attributed to the down‐conversion luminescence effect by Eu³⁺ ions from ultraviolet light to visible light and up‐conversion luminescence effect by Er³⁺ ions from infrared light to visible light.     

Oxygenated-graphene-enabled recombination barrier layer for high performance dye-sensitized solar cell

Wide-bandgap multilayer oxygenated graphene (MLOG) is used as the recombination barrier layer (RBL) in dye-sensitized solar cell (DSSC). The MLOG is derived from multilayer graphene synthesized by chemical vapor deposition (CVD) and oxygenated with high density/low power oxygen plasma. We observe 19% improvement in photoconversion efficiency of the DSSC with MLOG RBL, as compared with DSSC without RBL. Lifetime of photo-injected electrons at the conduction band of TiO₂ nanoparticle electrode is increased due to the presence of MLOG. This is attributed to effective collection of electrons at the transparent conductor electrode by suppressing interfacial-recombination via TiO₂ surface states. The control over dark current of the DSSC is also significantly enhanced with MLOG as compared with that without RBL as the direct result of improved interfacial quality of the TiO₂/dye/electrolyte structure.     

Chlorophyll assembled electrode for photovoltaic conversion device

Chlorophyll-a (Chl-a) assembled in hydrophobic domain by fatty acid with long alkyl hydrocarbon chain such as myristic acid (Myr), stearic acid (Ste) and cholic acid (Cho) modified onto nanocrystalline TiO₂ electrode is prepared and the photovoltaic properties of the nanocrystalline TiO₂ film by Chl-a are studied. Incident photon to current efficiency (IPCE) value at 660 nm in photocurrent action spectrum of Chl-a/Ste-TiO₂, Chl-a/Myr-TiO₂ and Chl-a/Cho-TiO₂ electrodes are 5.0%, 4.1% and 4.1%, respectively. Thus, the IPCE is maximum using Chl-a/Ste-TiO₂ electrode. From the results of photocurrent responses with light intensity of 100 mW cm⁻² irradiation or monochromatic light with 660 nm, generated photocurrent increases using Chl-a/Ste-TiO₂ electrode compared with the other Chl-a assembled TiO₂ electrodes. These results show that the hydrophobic domain formed by stearic acid with long alkyl hydrocarbon chain is suitable for fixation of Chl-a onto TiO₂ film electrodes and photovoltaic performance is improved using Chl-a onto Ste-TiO₂ film electrode.     

Fabrication of Three-Dimensionally Ordered Macroporous TiO2 Films with Enhanced Photovoltaic Conversion Efficiency

Negative-charged polystyrene (PS) microspheres were prepared through a soap-free emulsion polymerization method using potassium persulfate as initiator. Three-dimensionally ordered macroporous TiO₂ films were fabricated using the high-quality PS colloidal crystals templates obtained via a horizontal deposition method. The as-prepared macroporous TiO₂ films were applied as the photoanodes in dye-sensitized solar cell (DSSC). The microstructure of the products were characterized by X-ray diffractometer, fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy and nitrogen adsorption–desorption analyzer. The results showed that the macroporous TiO₂ films replicated well the 3D ordered structure derived from PS colloidal crystal templates and revealed a relatively large specific surface area (69.99 m²/g), which could increase the capacity of TiO₂ film anode for absorbing dyes and scattering light. The photocurrent–voltage (I–V) characteristics of DSSC were measured by a digital source meter under simulated solar light. The results indicated that the introduction of an ordered macroporous TiO₂ interfacial layer increased the photovoltaic conversion efficiency, which was improved by 68 % from 3.61 to 6.08 %, as compared to a device using a bare P25 TiO₂ photoanode. Our results showed that the hierarchically ordered macroporous TiO₂ bilayer films photoanode for DSSC could be helpful to improve the photovoltaic conversion efficiency.     

Photovoltaic efficiency on dye-sensitized solar cells (DSSC) assembled using Ga-incorporated TiO2 materials

This study examined the photoelectric conversion efficiency of DSSC (dye-sensitized solar cell) when nanometer sized Ga (0.25, 0.50, and 1.00 mol%)–TiO₂ prepared using a hydrothermal method was employed as a working electrode material. The particle sizes observed in the transmission electron microscopy images were <20 nm in all samples. However, with increasing Ga concentration, the size increased and the shapes transformed to a stick form. The absorption band was slightly blue-shifted upon the incorporation of gallium ions, but the intensity of the photoluminescence (PL) curves of the Ga-incorporated TiO₂ was significantly smaller, with the smallest case being the 0.50 mol% Ga–TiO_2, which was related to recombination between the excited electrons and holes. When Ga–TiO₂ was applied in DSSC, the energy conversion efficiency was enhanced considerably compared to that using pure TiO₂; it was approximately 4.57% with the N3 dye under 100 mW/cm² of simulated sunlight. These results are in agreement with an electrostatic force microscopy (EFM) study showing that the electrons were transferred rapidly to the surface of Ga–TiO₂ film, compared with that on a pure TiO₂ film.     

TiO2–BaTiO3 nanocomposite for electron capture in dye‐sensitized solar cells

Different compositions of TiO₂–BaTiO₃ nanocomposites are synthesized with various weight ratios for dye‐sensitized solar cell (DSSC) applications. TiO₂ and BaTiO₃ nanoparticles (NPs) are synthesized by sol‐gel and solvothermal methods, respectively and are employed as the photoanode electrodes. BaTiO₃ NPs have pure cubic perovskite crystal structure with an average size of 20‐40 nm, while TiO₂ NPs show pure anatase phase with 15‐30 nm size. The power conversion efficiency (PCE) enhancement of the cells is first attained by controlling the thickness of the films for light harvesting improvement. The fabricated DSSC composed of pure BaTiO₃ NPs with an optimal thickness of 25 μm shows efficiency of 6.83%, whereas that made of pure TiO₂ NPs with 14 μm thickness has cell efficiency of 7.24%. Further improvement of cell efficiency is achieved by preparation of binary oxide nanocomposites using TiO₂ and BaTiO₃ NPs with various weight ratios. The highest PCE of 9.40% is obtained for the nanocomposite with TiO₂:BaTiO₃=85:15 (wt%). The enhancement is assigned to less recombination of photo‐generated electrons and higher incident photon to current conversion yield as a result of rapid charge collection and higher dye sensitization.     

Enhancing photovoltaic performance of dye-sensitized solar cell by rare-earth doped oxide of Lu2O3:(Tm, Yb)

In order to increase of the photocurrent, photovoltage and energy conversion efficiency of dye-sensitized solar cell (DSSC), rare-earth doped oxide of Lu₂O₃:(Tm³⁺, Yb³⁺) is prepared and introduced into the TiO₂ film in the DSSC. As a luminescence medium, Lu₂O₃:(Tm³⁺, Yb³⁺) improves incident light harvest via a conversion luminescence process and increases photocurrent; as a p-type dopant, the rare-earth ions elevate the energy level of the oxide film and increase the photovoltage. Under a simulated solar light irradiation of 100 mW cm⁻², the light-to-electric energy conversion efficiency of the DSSC with Lu₂O₃:(Tm³⁺, Yb³⁺) doping reaches 6.63%, which is increased by 11.1% compared to the DSSC without Lu₂O₃:(Tm³⁺, Yb³⁺) doping.     

Polyvinyl pyrrolidone aided preparation of TiO2 films used in flexible dye-sensitized solar cells

Polyvinyl pyrrolidone (PVP) is introduced to low temperature preparation of a good quality TiO₂ film used in flexible dye-sensitized solar cells (DSSCs). The samples are characterized by scanning electron microscopy and UV–vis absorption spectra, the photovoltaic performance of the DSSC is measured. It is found that PVP can improve the dispersion of TiO₂ particles and the adherence of TiO₂ particles to flexible substrate, as well as the adsorption of sensitized dye to TiO₂ film. Additionally, ultraviolet light irradiation can eliminate organics remained on the surface the TiO₂ film and improve the surface state of TiO₂ film. Under an optimal condition, a flexible DSSC using TiO₂ film doped PVP and UV irradiation treated achieves a light-to-electric energy conversion efficiency of 3.02% under irradiation with a simulate solar light intensity of 100 mW cm⁻².     

Mesoporous nitrogen-doped TiO2 sphere applied for quasi-solid-state dye-sensitized solar cell

A mesoscopic nitrogen-doped TiO₂ sphere has been developed for a quasi-solid-state dye-sensitized solar cell [DSSC]. Compared with the undoped TiO₂ sphere, the quasi-solid-state DSSC based on the nitrogen-doped TiO₂ sphere shows more excellent photovoltaic performance. The photoelectrochemistry of electrodes based on nitrogen-doped and undoped TiO₂ spheres was characterized with Mott-Schottky analysis, intensity modulated photocurrent spectroscopy, and electrochemical impedance spectroscopy, which indicated that both the quasi-Fermi level and the charge transport of the photoelectrode were improved after being doped with nitrogen. As a result, a photoelectric conversion efficiency of 6.01% was obtained for the quasi-solid-state DSSC.     

Low temperature preparation of a high performance Pt/SWCNT counter electrode for flexible dye-sensitized solar cells

A platinum/single-wall carbon nanotube (Pt/SWCNT) film was sprayed onto a flexible indium-doped tin oxide coated polyethylene naphthalate (ITO/PEN) substrate to form a counter electrode for use in a flexible dye-sensitized solar cell using a vacuum thermal decomposition method at low temperature (120 °C). The obtained Pt/SWCNT electrode showed good chemical stability and light transmittance and had lower charge transfer resistance and higher electrocatalytic activity for the I₃⁻/I⁻ redox reaction compared to the flexible Pt electrode or a commercial Pt/Ti electrode. The light-to-electric energy conversion efficiency of the flexible DSSC based on the Pt/SWCNT/ITO/PEN counter electrode and the TiO₂/Ti photoanode reached 5.96% under irradiation with a simulated solar light intensity of 100 mW cm⁻². The efficiency was increased by 25.74% compared to the flexible DSSC with an unmodified Pt counter electrode.     

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.     

Fabrication and photoelectrochemical properties of TiO2 films on Ti substrate for flexible dye-sensitized solar cells

The dye-sensitized solar cells (DSSCs) using Ti foil supporting substrate for fabricating nanocrystalline TiO₂ flexible film electrodes were developed, intending to improve the photoelectrochemical properties of flexible substrate-based DSSCs. The obtained cells were characterized by electrochemical impedance spectra (EIS), open circuit voltage decay (OCVD) measurement and Tafel plots. The experimental results indicate that the most important advantage of a Ti foil-based TiO₂ flexible electrode over a FTO glass-based electrode lies in its reduced sheet resistance, electron traps, and the retarded back reaction of electrons with tri-iodine ions in DSSCs. All above characteristics for the Ti substrate TiO₂ films are beneficial for decreasing the charge recombination in the TiO₂ electrode and prolonging the electron lifetimes for the DSSCs, as well as improvement of the overall solar conversion efficiency. The photocurrent of the cell fabricated with the Ti foil-based flexible electrode increased significantly, leading to a much higher overall solar conversion efficiency of 5.45% at 100 mW/cm² than the cell made with FTO glass-based TiO₂ electrodes. Above results demonstrate that Ti foil is a potential alternative to the conventional FTO glass substrate for the DSSCs.     

Fabrication of hole-patterned TiO2 photoelectrodes for solid-state dye-sensitized solar cells

We suggest a simple process to fabricate a hole-patterned TiO₂ electrode for a solid-state dye-sensitized solar cell (DSSC) to enhance cell performance through interfacial properties of the electrode with the electrolyte with minimum dye loading. The method involves prepatterning of SU-8 photoresist on a conducting glass, followed by the deposition of a nanocrystalline TiO₂ layer, calcination at 450 °C and characterization using scanning electron microscopy (SEM). Hole-patterned TiO₂ photoelectrodes yielded better solar energy conversion efficiency per dye loading compared to a conventional non-patterned photoelectrode. For example, a 50 μm hole-patterned DSSC exhibited 4.50% conversion efficiency in the solid state, which is comparable to an unpatterned flat TiO₂ photoelectrode (4.57%) however the efficiency per dye loading of the former (0.986%/g) was much greater than that of the latter (0.898%/g). The improvement was attributed to improved transmittance through the electrode as well as better interfacial properties between the electrolyte and electrode, as confirmed by UV-visible spectroscopy and electrochemical impedance (EIS) analysis.     

Enhanced photoelectric efficiency by surface modification of TiO<Subscript>2</Subscript> thin film using various acidic species

This study examined the photoelectric conversion efficiency of the dye-sensitized solar cell (DSSC) when the surface of a nanometer-sized TiO₂ film, which was prepared using the solvothermal method, was modified by five acid compounds. The TiO₂ film exhibited an anatase structure with an average particle size in the range of 10–15 nm, and the maximum absorption band was shown in the UV-visible spectrum around 360 nm. The surface colors of the carboxylic acid-modified TiO₂ films were changed to light or dark with differing energy conversion efficiencies. Particularly, the conversion efficiency was considerably enhanced from approximately 6.25% for the non-modified TiO₂ film to approximately 7.50% for the film treated by acetic acid of 1.0 mole, with the N719 dye under 100 mW/cm² of simulated sunlight. FT-IR analysis of the films after N719 dye adsorption confirmed that the IR spectrum of the modified TiO₂ showed a sharp and strong band at 500 cm⁻¹, which was assigned to a metal-O bond, due to the formation of a new Ti-O bond between the O of COO⁻ and the Ti atom, which was relatively weaker in the non-modified TiO₂. Furthermore, these results were in agreement with an electrostatic force microscopy (EFM) study showing that the electrons were transferred rapidly to the surface of the acetic acid-modified TiO₂ film, compared with that on the nonmodified TiO₂ film.     

Solid‐state dye‐sensitized and bulk heterojunction solar cells using TiO2 and ZnO nanostructures: recent progress and new concepts at the borderline

In the field of photovoltaic energy conversion, hybrid inorganic/organic devices represent promising alternatives to standard photovoltaic systems in terms of exploiting the specific features of both organic semiconductors and inorganic nanomaterials. Two main categories of hybrid solar cells coexist today, both of which make much use of metal oxide nanostructures based on titanium dioxide (TiO₂) and zinc oxide (ZnO) as electron transporters. These metal oxides are cheap to synthesise, are non‐toxic, are biocompatible and have suitable charge transport properties, all these features being necessary to demonstrate highly efficient solar cells at low cost. Historically, the first hybrid approach developed was the dye‐sensitized solar cell (DSSC) concept based on a nanostructured porous metal oxide electrode sensitized by a molecular dye. In particular, solid‐state hybrid DSSCs, which reduce the complexity of cell assembly, demonstrate very promising performance today. The second hybrid approach exploits the bulk heterojunction (BHJ) concept, where conjugated polymer/metal oxide interfaces are used to generate photocurrent. In this context, we review the recent progress and new concepts in the field of hybrid solid‐state DSSC and BHJ solar cells based on TiO₂ and ZnO nanostructures, incorporating dyes and conjugated polymers. We point out the specificities in common hybrid device structures and give an overview on new concepts, which couple and exploit the main advantages of both DSSC and BHJ approaches. In particular, we show that there is a trend of convergence between both DSSC and BHJ approaches into mixed concepts at the borderline which may allow in the near future the development of hybrid devices for competitive photovoltaic energy conversion. Copyright © 2011 Society of Chemical Industry     

Pore size dependence of self-assembled type photonic crystal on dye-sensitized solar cells efficiency utilising Chlorine e6

There are few reports on photoelectric conversion efficiency using naturally-occurring dyes for dye-sensitized solar cells (DSSC). This is because the matching with an excited electronic level of naturally-occurring dye to the conduction band of semiconductor is problematic; the excited electrons are easily relaxed to the steady state with fluorescence or heat emission. We examined the fluorescence inhibition effect of a self-assembled photonic crystal using Chlorine e6 dye. Chlorine e6 is derived from chlorophyll and has a long excited electron lifetime. We prepared TiO₂ inverse opals with various particle sizes by liquid phase deposition and described their effect on DSSCs with regard to structural, optical and electrochemical properties. In addition, we explored the implications of fluorescence lifetime measurements relative to the photonic band diagram and the amount of adsorbed dye. Although the main factor affecting the external photoelectric conversion efficiency was the diffusion resistance of the electrolyte and the contact resistance between TiO₂ interfaces, the possibility that the dye fluorescence lifetime, i.e. the photonic band structure, can affect the internal quantum efficiency per one dye molecule was also investigated.     

Effect of side chain substituents on the electron injection abilities of unsymmetrical perylene diimide dyes

Three near-infrared (NIR) absorbing unsymmetrical perylene diimide D-A-D type dyes containing 6-undecanoxy as donor group were utilized in dye-sensitized nanocrystalline TiO₂ solar cells. Structure of the acceptor side of the molecules were improved by adding 4-[2-methyl-5-(cyanoacrylic acid)-3-thienyl]-phenyl (V), 3-carboxy-2-pyridil (VI) and 3-carboxy-2-pyrazyl (VII) moieties attached to one of the N-side of the dye. The relationship between the molecular structure of the acceptor sites of the dyes and the photovoltaic performances were discussed. Electrochemical measurements indicated that band gaps of the dyes were energetically favorable for electron injection from the excited state of the dyes to the conduction band of TiO₂ nanoparticles. However, three dyes gave lower conversion efficiency on DSSC applications. Strong electron-withdrawing nature of perylene core might not permit to transfer the photo-generated electrons to the carboxyl groups anchoring to TiO₂ surface, and then solar-to-electricity conversion efficiencies of the dyes were reduced.