Catalytic materials manufactured by the polyol process for monolithic dye‐sensitized solar cells

Three types of screen‐printable catalytic pastes were successfully prepared to be used as counterelectrode for monolithic dye solar cells encapsulated with glass frit. The electroless bottom‐up method or so‐called polyol process has been applied to fabricate thermally stable SnO₂:Sb/Pt and carbon black/Pt nanocomposites. The catalytic and electric properties of these materials were compared with a new platinum‐free type of carbon counterelectrode. The layers containing low platinum amounts (less than 5 µg/cm²) exhibit a very low charge transfer resistance of about 0·4 Ω · cm². Also the conductive carbon layer shows an acceptable charge transfer resistance of 1·6 Ω · cm². Additionally the catalytic layer containing porous carbon black reveals excellent sheet resistance below 5 Ω/□; this feature has enabled to work out a low cost counterelectrode which combined suitable catalytic and conductive properties. The layers have been characterized using following methods: electrochemical impedance spectroscopy (EIS), field emission scanning electron microscopy (FE‐SEM), energy filter transmission electron microscopy (EF‐TEM) and inductively coupled plasma mass spectroscopy (ICP‐MS). Copyright © 2008 John Wiley & Sons, Ltd.     

Parallel‐connected monolithic dye‐sensitised solar modules

Light‐soaking and high‐temperature storage testing of monolithic dye‐sensitised solar modules with total area module efficiencies above 5% have been performed. Our experiences from the development of a four‐layer monolithic dye‐sensitised solar test cell for comparative testing of material components for dye‐sensitised solar cells have directed our module development to a novel device design consisting of parallel‐connection of individual monolithic cells. The results from the accelerated testing of the modules (total area of 17.0 cm²) with four parallel‐connected cells (active area of 3.38 cm²/cell) are equivalent to those obtained for the monolithic single test cells when using identical device components. The successful transfer from cell to module stability is an important milestone in our ambition to develop a low‐cost Photovoltaic (PV) technology. Moreover, our results indicate that intensified research and development to define the procedures for relevant accelerated testing of dye‐sensitised solar modules is urgently required. Copyright © 2010 John Wiley & Sons, Ltd.     

Nanocrystalline dye‐sensitized solar cells having maximum performance

This paper presents an overview of the research carried out by a European consortium with the aim to develop and test new and improved ways to realise dye‐sensitized solar cells (DSC) with enhanced efficiencies and stabilities. Several new areas have been explored in the field of new concepts and materials, fabrication protocols for TiO₂ and scatterlayers, metal oxide blocking layers, strategies for co‐sensitization and low temperature processes of platinum deposition. Fundamental understanding of the working principles has been gained by means of electrical and optical modelling and advanced characterization techniques. Cost analyses have been made to demonstrate the potential of DSC as a low cost thin film PV technology. The combined efforts have led to maximum non‐certified power conversion efficiencies under full sunlight of 11% for areas <0ċ2 cm² and 10ċ1% for a cell with an active area of 1ċ3 cm². Lifetime studies revealed negligible device degradation after 1000 hrs of accelerated tests under thermal stress at 80°C in the dark and visible light soaking at 60°C. An outlook summarizing future directions in the research and large‐scale production of DSC is presented. Copyright © 2006 John Wiley & Sons, Ltd.     

An efficient titanium‐based photoanode for dye‐sensitized solar cell under back‐side illumination

Pretreatment of H₂O₂ is performed on titanium (Ti) foil as an efficient photoanode substrate for dye‐sensitized solar cell (DSSC). The H₂O₂‐treated Ti shows high surface area because of the formation of networked TiO₂ nanosheets, which enhances electrical contact between screen‐printed TiO₂ nanoparticles and Ti foil. Electron transfer on the photoanode is improved, as identified by reduced charge transfer resistance and improved electron transport properties. Compared with DSSC based on non‐treated Ti photoanode, DSSC with this H₂O₂‐treated Ti photoanode exhibits remarkable increases in short‐circuit current density (from 8.55 to 14.38 mA/cm²) and energy conversion efficiency (from 4.68 to 7.10%) under AM1.5 back‐side illumination. Copyright © 2011 John Wiley & Sons, Ltd.     

Large area dye‐sensitized solar cells: material aspects of fabrication

Dye‐sensitized photoelectrochemical solar cells of large area are fabricated using highly conducting and optically transparent glass consisting of an inner layer of indium‐tin oxide and an outer layer of fluorine doped tin oxide. A method is described for the deposition of nanocrystalline films of TiO₂ consisting of large and small median size particles (30 and 5 nm, respectively) which promote porosity and light scattering. Incorporation of trace quantities of magnesium oxide into TiO₂ increased the efficiency of the cells. The energy conversion efficiency of a cell (AM 1·5, 1000 W m⁻² simulated sunlight) of area 21 cm² was found to be 7·2% compared to 5·6% in the absence of magnesium oxide. The mechanisms by which the magnesium oxide improves the cell performance are discussed. Copyright © 2006 John Wiley & Sons, Ltd.     

Toward high‐efficiency dye‐sensitized solar cells with a photoanode fabricated via a simple water‐based formulation

An aqueous formulation containing commercially available P25 nanoparticles and a water‐soluble precursor—titanium (IV) bis(ammonium lactato)dihydroxide (TALH) has been developed and optimized for fabricating photoanodes in dye‐sensitized solar cells. An optimal formulation achieved a power conversion efficiency of 9.2%. Solar cell performance is significantly influenced by precursor concentration impacting the porosity and electron transport of the thin film. The use of TALH during processing is shown to enhance the electron transport in the resulting titanium dioxide nanoparticle network using transient decay measurements. Bridging between neighboring nanoparticles is confirmed using transmission electron microscopy explaining the enhanced electron transport. The developed formulation has several advantages, as it is water‐based, composed of inexpensive, non‐hazardous components, is easy to make, and does not require special handling. The formulation has great potential for industrial applications, in particular for DSC manufacturing using roll‐to‐roll technology. Copyright © 2014 John Wiley & Sons, Ltd.     

Photovoltaic characterization of dye‐sensitized solar cells: effect of device masking on conversion efficiency

We analyze the effect of masking on the conversion efficiency of dye sensitized solar cells (DSC) by comparing the photovoltaic performance of the device subjected to light from a solar simulator for a variety of mask sizes. The aperture size of the mask had a significant effect on the energy conversion efficiency, which varied by as much as 36%. We identify factors that contribute to measurement errors and propose optimal conditions for the characterization of DSC's of small size. Copyright © 2006 John Wiley & Sons, Ltd.     

The use of Ti meshes with self‐organized TiO2 nanotubes as photoanodes of all‐Ti dye‐sensitized solar cells

This paper reports a simple and facile method for directly growing self‐organized TiO₂ nanotubular arrays around the whole Ti mesh by electrochemical anodization in organic electrolytes and their application in all‐Ti dye‐sensitized solar cells (DSSCs). Compared with the traditional fluorine‐doped tin oxide (FTO)‐based DSSC and the backside illuminated DSSC, this type of DSSC showed advantages such as low resistance, cheap fabrication cost and enhanced sunlight utilization. Different thicknesses of nanotubular array layers were investigated to find their influence on the photovoltaic parameters of the cell. We also considered three types of meshes as the substrates of anodes and found that the cell with 6 openings/mm² exhibited the highest conversion efficiency of 5.3%. The area of the cell had only a little impact on the photovoltaic performances. Copyright © 2010 John Wiley & Sons, Ltd.     

Coral‐shaped ZnO nanostructures for dye‐sensitized solar cell photoanodes

A highly efficient ZnO photoanode for dye‐sensitized solar cells was successfully grown by a simple, low cost, and scalable method. A nanostructured coral‐shaped Zn layer was deposited by sputtering onto fluorine‐doped tin oxide/glass slices at room temperature and then thermally oxidized in ambient atmosphere. Stoichiometry, crystalline phase, quality, and morphology of the film were investigated, evidencing the formation of a highly porous branched nanostructure, with a pure wurtzite crystalline structure. ZnO‐based dye‐sensitized solar cells were fabricated with customized microfluidic architecture. Dye loading on the oxide surface was analyzed with ultraviolet‐visible spectroscopy, and the dependence of the cell efficiency on sensitizer incubation time and film thickness was studied by current‐voltage electrical characterization, incident photon‐to‐electron conversion efficiency, and impedance spectroscopy measurements, showing the promising properties of this material for the fabrication of dye‐sensitized solar cell photoanodes with a solar conversion efficiency up to 4.58%. Copyright © 2012 John Wiley & Sons, Ltd.     

Electrochemical synthesis of a double‐layer film of ZnO nanosheets/nanoparticles and its application for dye‐sensitized solar cells

A double‐layer film, consisting of an upper layer of ZnO nanosheets and a lower layer of ZnO nanoparticles (designated as ZnONS/NP), was synthesized for the photoanode of a dye‐sensitized solar cell (DSSC) by a one‐step potentiostatic electrodeposition on a conducting fluorine‐doped tin oxide substrate at 70 °C in a solution containing zinc nitrate and sodium acetate, followed by the pyrolysis of the film at 300 °C. The growth mechanism of the double‐layer nanostructure was studied by monitoring the morphological changes at various periods of electrodeposition. The effects of the concentration of acetate anion on the morphology of the double‐layer structure were also studied. The double‐layer film of ZnONS/NP showed a better self‐established light scattering property, compared with that of a thin film of ZnO nanoparticles, prepared without acetate anion. The concentration of an acetate anion in the electrolyte for the electrodeposition of the double‐layer film, the electrodeposition period, and the period for dye adsorption were optimized for obtaining the best performance for a DSSC with a photoanode consisting of the double layer. A metal‐free dye, coded as D149, was used in this research. A conversion efficiency of 4.65% was achieved for a DSSC (0.2376 cm²) with the photoanode, consisting of the double‐layer film, under 100 mW/cm² illumination in the wavelength range of 400–800 nm. X‐ray diffraction patterns, thermo gravimetric curves, elemental analysis, scanning electron microscopic images, transmission electron microscopic image, transmission spectra, and electrochemical impedance spectra were used to explain observations. Copyright © 2012 John Wiley & Sons, Ltd.     

Enhanced photovoltaic performance of cross‐linked ruthenium dye with functional cross‐linkers for dye‐sensitized solar cell

Photovoltaic performance of cross‐linkable Ru(2,2′‐bipyridine‐4,4′‐bicarboxylic acid)(4,4′‐bis((4‐vinyl benzyloxy)methyl)‐2,2′‐bipyridine)(NCS)₂ (denoted as RuS dye) adsorbing on TiO₂ mesoporous film was enhanced by polymerizing with either ionic liquid monomer, 1‐(2‐acryloyloxy‐ethyl)‐3‐methyl‐imidazol‐1‐ium iodide (AMImI), to form RuS‐cross‐AMImI or di‐functional acrylic monomer with ether linkage, triethyleneglycodimethacrylate (TGDMA), to form RuS‐cross‐TGDMA. Their cross‐linking properties were investigated by UV–vis spectroscopy by rinsing with 0.1 N NaOH aqueous solution. The power conversion efficiencies (PCEs) of dye‐sensitized solar cells (DSSCs) with RuS‐cross‐AMImI and RuS‐cross‐TGDMA both reached over 8% under standard global air mass 1.5 full sunlight. The increased PCE for DSSCs with RuS‐cross‐AMImI comparing with cross‐linked RuS was attributed to the I⁻ counterion of AMImI increasing the charge regeneration rate of RuS dye, whereas that with RuS‐cross‐TGDMA was attributed to the Li⁺ coordination property of TGDMA. The photovoltaic performance of RuS‐cross‐TGDMA was also slightly better than that of RuS‐cross‐AMImI because of higher open‐circuit photovoltage (V_oc) and short‐circuit photocurrent (J_sc). Its higher V_oc was supported by the Bode plot of impedance under illumination and Nyquist plots at dark, whereas higher J_sc was supported by the incident monochromatic photon‐to‐current conversion efficiency spectra and charge extraction experiments. Copyright © 2013 John Wiley & Sons, Ltd.     

Transparent conductive oxide‐less back contact dye‐sensitized solar cells using cobalt electrolyte

Transparent conductive oxide‐less (TCO‐less) dye‐sensitized solar cells (DSSCs) have been fabricated and characterized using nanoporous TiO₂‐coated stainless steel metal mesh as flexible photoanode and cobalt bipyridyl complex (Co(bpy))‐based one electron redox shuttle electrolyte. Attempts have been made towards enhancing the efficiency of TCO‐less DSSCs to match with their TCO‐based DSSC counterparts. It has been found that surface protection of metal mesh is highly required for enhancing the efficiency of TCO‐less DSSCs specially using cobalt electrolytes as confirmed by dark current–voltage characteristics. Photocurrent action spectra clearly reveal that TCO‐based DSSCs using (Co(bpy)) electrolyte exhibits photon harvesting (incident photon to current conversion efficiency (IPCE) 52%) in the 370–450 nm wavelength region as compared to photon harvesting at peak absorption of the dye (IPCE 56% at 550 nm), which is almost the same (IPCE 47%) in the 400–610 nm wavelength region for TCO‐less DSSCs. Under similar experimental conditions, replacing indoline dye D‐205 to porphyrin‐based dye YD2‐o‐C8 led to the enhancement in the photoconversion efficiency from 3.33% to 4.84% under simulated solar irradiation. Copyright © 2014 John Wiley & Sons, Ltd.     

Ultrafast near infrared sintering of TiO2 layers on metal substrates for dye‐sensitized solar cells

A limiting step to roll‐to‐roll production of dye‐sensitized solar cells on metals is TiO₂ sintering (10–30 min). Near infrared (NIR) heating is a novel process innovation which directly heats titanium substrates giving rapid binder removal and sintering. NIR heating (for 12.5 s) at varying power gave titanium temperatures of 545, 685 and 817°C yielding cells with efficiencies of 2.9, 2.8 and 2.5%. Identical cells prepared in a conventional oven (1800 s) at 500, 600 and 800°C gave 2.9, 2.6 and 0.2% efficiency. NIR sintering is ultrafast and has a wide process window making it ideal for rapid manufacturing on metals. Copyright © 2010 John Wiley & Sons, Ltd.     

Highly efficient dye‐sensitized solar cells using phenothiazine derivative organic dyes

Two novel organic dyes have been synthesized using electron rich phenothiazine as electron donors and oligothiophene vinylene as conjugation spacers. The two dyes (2E)‐2‐cyano‐3‐(5‐(5‐((E)‐2‐(10‐(2‐ethylhexyl)‐10H‐phenothiazin‐7‐yl)vinyl)thiophen‐2‐yl)thiophen‐2‐yl)acrylic acid (PTZ‐1) and (2E)‐3‐(5‐(5‐(4,5‐bis((E)‐2‐(10‐(2‐ethylhexyl)‐10H‐phenothiazin‐3‐yl)vinyl)thiophen‐2‐yl)thiophen‐2‐yl)thiophen‐2‐yl)‐2‐cyanoacrylic acid (PTZ‐2) were fully characterized and employed in dye‐sensitized solar cells (DSCs) to explore the effect of disubstituted donors on photovoltaic (PV) performance. The solar cells sensitized by the PTZ1 dye have a high IPCE plateau of 80% and achieve a short‐circuit photocurrent density of 12.98 mA/cm², an open‐circuit voltage of 0.713 V, and a fill factor (ff) of 66.6%, corresponding to a conversion efficiency of 6.17% under AM 1.5 100 mW/cm² illumination. The different performance of the solar cells based on the two dyes can be understood from the studies of the electron kinetics by electrochemical impedance spectroscopy (EIS). These investigations reveal that disubstituted donors in the organic sensitizers of three or more conjugation units deteriorate the PV performance due to enhanced recombination. Copyright © 2010 John Wiley & Sons, Ltd.     

Design of conduction band structure of TiO2 electrode using Nb doping for highly efficient dye‐sensitized solar cells

A barrier layer of undoped TiO₂ was deposited on the Nb‐doped TiO₂ electrode to suppress the recombination at the Nb‐doped TiO₂/dye–electrolyte interface for highly efficient dye‐sensitized solar cells (DSCs). The Nb content in TiO₂ was varied in a range of 0.7–3.5 mol% to modify the TiO₂ energy‐band structure. Nb‐doped TiO₂/dye interfaces were characterized by a combination of ultraviolet photoemission spectroscopy and optical absorption spectroscopy measurements, allowing the determination of the conduction band minimum (CBM) of the TiO₂ electrode and the lowest unoccupied molecular orbital of the N719 dye. The lowering of TiO₂ CBM by Nb doping induced the increase in short‐circuit current of DSCs. However, open‐circuit voltage and fill factor are decreased, and this result was ascribed to the enhanced recombination at the Nb‐doped TiO₂/dye–electrolyte interface. The effect of doping on charge transport in DSCs was analyzed using electrochemical impedance spectroscopy. We have shown that by introducing of TiO₂ barrier layer, the Nb doping content, which results in DSC highest efficiency, can be increased because of the suppression of the dopant‐induced recombination. The energy conversion efficiency of the solar cells increased from 7.8% to 9.0% when undoped TiO₂ electrode is replaced with electrode doped with 2.7 mol% of Nb because of the improvement of the electron injection and collection efficiencies. The correlation between the electronic structure of the TiO₂ electrode, charge transfer characteristics, and photovoltaic parameters of DSCs is discussed. Copyright © 2012 John Wiley & Sons, Ltd.     

Enhanced efficiency of phenothiazine derivative organic dye‐sensitized ionic liquid solar cells on aging

We have used electrochemical impedance to investigate the improvement in photovoltaic performance in aging of ionic liquid dye‐sensitized solar cells using a high‐absorption coefficient organic dye (2E)‐2‐cyano‐3‐(5‐(5‐((E)‐2‐(10‐(2‐ethylhexyl)‐10H‐phenothiazin‐7‐yl)vinyl)thiophen‐2‐yl)thiophen‐2‐yl)acrylic acid, which is in contrast to N719‐based devices. It was found that the enhancement is due to reduced recombination of the photoexcited electrons. The decreased recombination plausibly originates from molecular re‐orientation along with cation adsorption, with Fourier transform infrared spectra lending support to the former mechanism. After aging, the photovoltaic device using the organic dye outperforms the counterpart by the ruthenium complex dye and achieves an impressive efficiency of 5.6% under AM 1.5 100 mW/cm² illumination. Copyright © 2011 John Wiley & Sons, Ltd.     

Low‐temperature flexible Ti/TiO2 photoanode for dye‐sensitized solar cells with binder‐free TiO2 paste

An energy‐economical dye‐sensitized solar cell (DSSC) with highly flexible Ti/TiO₂ photoanode was developed through a low‐temperature process, using a binder‐free TiO₂ paste. Ti foils, coated with the binder‐free TiO₂ films were annealed at various temperature. Scanning electron microscopic (SEM) images of the films show uniform, mesoporous and crack‐free surface morphologies as well as interpenetrated TiO₂ network. DSSCs with binder‐free TiO₂ films annealed at 450, 350, 250 and 120°C show solar‐to‐electricity conversion efficiencies (η) of 4.33, 4.34, 3.72 and 3.40%, respectively, which are comparable to the efficiency of 4.56% obtained by using a paste with binder and annealing it at 450°C; this observation demonstrates the benefits of a binder‐free TiO₂ paste for the fabrication of energy‐fugal DSSCs. On the other hand, when organic binder was used in the TiO₂ paste for film preparation, a drastic deterioration in the cell performance with decreasing annealing temperature is noticed. Laser‐induced photo‐voltage transient technique is used to estimate the electron lifetime in various Ti/TiO₂ films. Electrochemical impedance spectroscopic (EIS) analysis shows that the lower the annealing temperature of the TiO₂ coated Ti foil, the larger the charge transfer resistance at the TiO₂/dye/electrolyte interface (R_ct2). Copyright © 2011 John Wiley & Sons, Ltd.     

Succinonitrile‐based solid‐state electrolytes for dye‐sensitised solar cells

Succinonitrile (SCN), a solid ion conductor (10⁻⁴ to 10⁻³ S/cm) in solid form at room temperature, is mixed with either 1,2‐dimethyl‐3‐propylimidazoliuum iodide or 1‐butyl‐3‐methyl imidazolium iodide ionic liquids for forming a solid plastic phase electrolyte for use in dye‐sensitised solar cell (DSSC). Cells containing these two electrolytes showed best energy conversion efficiencies of 6.3% and 5.6%, respectively. The commonly used DSSC electrolyte additives inhibit the formation of the SCN plastic phase. However, for the first time, an SCN‐additive (additive = guanidinium thiocyanate) electrolyte composition is reported here, which remains as a solid at room temperatures. By using these new solid electrolytes, a simple and rapid single‐step filling procedure for making solid‐state DSSC is outlined. This process, which reduces the required manufacturing steps from four to one, is most suitable for continuous, high‐throughput, commercial DSSC manufacturing lines. These new electrolytes have been tested under low incident light levels (200 lx) to investigate their suitability for indoor DSSC applications. Copyright © 2013 John Wiley & Sons, Ltd.     

Electroluminescence as a spatial characterisation technique for dye‐sensitised solar cells

In this study, electroluminescence as a spatial characterisation technique is used to characterise a 6.9% efficient dye‐sensitised solar cell. The obtained image is compared with a light beam‐induced current scan image and a transmittance image. Results reveal the presence of inhomogeneities including those resulting from the topography of the cell and from defects, for example, presence of iodine crystals in the electrolyte, localised absence of dye in the active layer and poor adhesion of the active layer to the electrodes. The ability to identify such inhomogeneities within a relatively short acquisition time gives electroluminescence an advantage over the light beam‐induced current technique. Copyright © 2012 John Wiley & Sons, Ltd.     

Processing and characterization of a TiO2 paste based on small particle size powders for dye‐sensitized solar cell semi‐transparent photo‐electrodes

The formulation and the preparation of a TiO₂ paste for dye‐sensitized solar cell technology are proposed. The TiO₂ paste is characterized in terms of rheology, morphology, cross section, specific surface area, and average pore size. A conversion efficiency of 7.42% without any chemical treatment or scattering layer was obtained using the optimal thickness of 11 µm as carried out in this work. The results over different batches of the paste confirm the stability and the reproducibility. The characterization of the TiO₂ semi‐transparent film is completed by investigating the dye adsorption saturation time after cyclic dye dipping steps through UV–Vis spectra measurements. Copyright © 2011 John Wiley & Sons, Ltd.