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.     

Rapid radiative platinisation for dye‐sensitised solar cell counter electrodes

The successful transition of dye‐sensitised solar cell (DSC) manufacture from laboratory to factory requires new thinking in terms of lowering cost and removing time consuming manufacturing process. Platinisation of the fluorine doped tin oxide (FTO) glass counter electrode is essential for the operation of a conventional DSC and is usually carried out by thermal decomposition of chloroplatinic acid at 385 °C for 30 min. Here, near infrared radiation is used to directly heat the FTO layer resulting in full platinisation in 12.5 s. These platinised electrodes behave identically to those produced via conventional static thermal treatment in assembled DSC devices. 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.     

Fabrication of screen‐printing pastes from TiO2 powders for dye‐sensitised solar cells

A preparation technique of TiO₂ screen‐printing pastes from commercially‐available powders has been disclosed in order to fabricate the nanocrystalline layers without cracking and peeling‐off over 17 µm thickness for the photoactive electrodes of the dye‐sensitised solar cells. A conversion efficiency of 8·7% was obtained by using a single‐layer of a semi‐transparent‐TiO₂ film. A conversion efficiency of 9·2% was obtained by using double‐layers composed of transparent and light‐scattering TiO₂ films for a photon‐trapping system. Copyright © 2007 John Wiley & Sons, Ltd.     

The monolithic multicell: a tool for testing material components in dye‐sensitized solar cells

A multicell is presented as a tool for testing material components in encapsulated dye‐sensitized solar cells. The multicell is based on a four‐layer monolithic cell structure and an industrial process technology. Each multicell plate includes 24 individual well‐encapsulated cells. A sulfur lamp corrected to the solar spectrum has been used to characterize the cells. Efficiencies up to 6·8% at a light‐intensity of 1000 W/m^su2 (up to 7·5% at 250 W/m²) have been obtained with an electrolyte solution based on γ‐butyrolactone. Additionally, a promising long‐term stability at cell efficiencies close to 5% at 1000 W/m² has been obtained with an electrolyte based on glutaronitrile. The reproducibility of the cell performance before and after exposure to accelerated testing has been high. This means that the multicell can be used as an efficient tool for comparative performance and stability tests. Copyright © 2006 John Wiley & Sons, Ltd.     

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.     

Cold isostatic pressing technique for producing highly efficient flexible dye‐sensitised solar cells on plastic substrates

One of the biggest challenges for making dye‐sensitised solar cells (DSCs) on plastic substrates is the difficulty in making good quality nanoporous TiO₂ films with both good mechanical stability and high electrical conductivity. Cold isostatic pressing (CIP) is a powder compaction technique that applies an isostatic pressure to a powder sample in all directions. It is particularly suitable for making thin films on plastic substrates, including non‐flat surfaces. Cold isostatically pressed nanocrystalline TiO₂ electrodes with excellent mechanical robustness were prepared on indium tin oxide (ITO)‐coated polyethylene naphthalate (PEN) substrates in the absence of organic binders and without heat treatment. The morphology and the physical properties of the TiO₂ films prepared by the CIP method were found to be very compatible with requirements for flexible DSCs on plastics. This room‐temperature processing technique has led to an important technical breakthrough in producing high efficiency flexible DSCs. Devices fabricated on ITO/PEN films by this method using standard P‐25 TiO₂ films with a Ru‐complex sensitiser yielded a maximum incident photon‐to‐current conversion efficiency of 72% at the wavelength of 530 nm and showed high conversion efficiencies of 6.3% and 7.4% for incident light intensities of 100 and 15 mW cm⁻², respectively, which are the highest power conversion efficiencies achieved so far for any DSC on a polymer substrate using the widely used, commercially available P‐25 TiO₂ powder. Copyright © 2011 John Wiley & Sons, Ltd.     

Development of Nano‐TiO2 dye sensitised solar cells on high mobility transparent conducting oxide thin films

The optical transmission of dye‐sensitised solar cells (DSCs) can be tuned by altering the dye and/or particle size of the mesoporous TiO₂ layers, to allow their application as the top device in tandem solar cells. To benefit from this semi‐transparency, parasitic optical losses by the transparent electrodes must be minimised. This work investigates the influence of using two different transparent conductors, namely, the high mobility material titanium doped indium oxide (ITiO) and fluorine doped tin oxide (FTO) as electrodes for semi‐transparent DSCs. The overall NIR transparency through the DSCs increased significantly as each FTO electrode was replaced by an ITiO electrode. This increase was from 20–45% in the 1300–700 nm wavelength range for fully FTO‐based cells, to about 60% for fully ITiO‐based cells, across the same spectrum. DSCs prepared on these electrodes exhibited short circuit currents ranging from 14·0–14·9 mA/cm². The conversion efficiency of the cell with ITiO as both the front and rear electrodes was 5·8%, which though significant, was lower than the 8·2% attained by the cell using FTO electrodes, as a result of a lower fill factor. Improvements in the ITiO thermal stability and in the processing of the TiO₂ interfacial layer are expected to improve the cell efficiency of such single DSC devices. The high current density and optical transparency of ITiO‐based DSCs make them an interesting option for tandem solar cells. Copyright © 2008 John Wiley & Sons, Ltd.     

Realization of high performance large area Z‐series‐interconnected opaque dye solar cell modules

We have designed and fabricated dye solar cell (DSC) modules with optimized geometries and processes. Integrated interconnections were made following the “Z” architecture for series connections. Several modules were prepared varying the materials, multilayer combination of the TiO₂ active layers, and the fabrication processes. With the best combination of TiO₂ multilayers, titanium tetrachloride (TiCl₄) treatment, a back reflector/diffusor, and optimized layout of cells via simulations, we fabricated a DSC module with a conversion efficiency of 6.9% on 43 cm² aperture area and 9.4% on active area. This result confirms that an effective scale‐up of high performance Z‐series‐connected DSC modules can be achieved comparable with other thin film technology. Note that the materials used to produce the devices of this work are all commercially available: an important result for a technology that is being developed for industrial application. Copyright © 2012 John Wiley & Sons, Ltd.     

New interdigital design for large area dye solar modules using a lead‐free glass frit sealing

A new interdigital design for large area dye solar modules is developed for an area of 30×30 cm². This design requires fewer holes in the glass substrate for electrolyte filling, than the conventional strip design. A complete manufacturing process of this module—ranging from screen printed layers to semi‐automated colouring and electrolyte filling—in a laboratory‐scale baseline is illustrated. As primary sealing method, a durable glass frit sealing is used. It is shown, that the lead (Pb) content present in many glass frit powders contaminates the catalytic platinum electrode during the sintering process, resulting in a lowering of the fill factor. A screen printable lead‐free glass frit paste is developed, which solves this problem. Long term stability tests are presented on 2·5 cm² dye solar cells, which have been completely sealed with glass frit. In consecutively performed accelerated ageing tests under 85°C in the dark (about 1400 h) and continuous illumination with visible light (1 sun, about 1700 h), a 2·5 cm² dye solar cell with an electrolyte based on propylmethylimidazolium iodide showed an overall degradation of less than 5% in conversion efficiency. In a subsequently performed thermal cycling test (−40°C to +85°C, 50 cycles) a 2·5 cm² dye solar cell with the same electrolyte composition also showed only a slight degradation of less than 5% in conversion efficiency. 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.     

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.     

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.     

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.     

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.     

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.     

Material development for dye solar modules: results from an integrated approach

In this paper, we report on the outcome of a German network project conducted with 12 partners from universities and research institutes on the material development of dye solar cells (DSC). We give an overview in the field and evaluate the concept of monolithic DSC further with respect to upscaling and producibility on glass substrates. We have developed a manufacturing process for monolithic DSC modules which is entirely based on screen printing. Similar to our previous experience gained in the sealing of standard DSC, the encapsulation of the modules is achieved in a fusing step by soldering of glass frit layers. For use in monolithic DSC, a platinum free, conductive counter electrode layer, showing a charge transfer resistance of R_CT < 1·5 Ω cm², has been realized by firing a graphite/carbon black composite under an inert atmosphere. Glass frit sealed monolithic test cells have been prepared using this platinum‐free material. A solar efficiency of 6% on a 2·0 cm² active cell area has been achieved in this case. Various types of non‐volatile imidazolium‐based binary ionic liquid electrolytes have been synthesized and optimized with respect to diffusion‐limited currents and charge transfer resistances in DSC. In addition, quasi‐solid‐state electrolytes have been successfully tested by applying inorganic (SiO₂) physical gelators. For the use in semi‐transparent DSC modules, a polyol process has been developed which resulted in the preparation of screen printed, transparent catalytic platinum layers showing an extremely low charge transfer resistance (0·25 Ω cm²). Copyright © 2008 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.     

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.