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DYE SENSITIZED SOLAR CELLS FOR THE BUILDING INTEGRATED PHOTOVOLTAIC MARKET
The present generation of solar cells rely on expensive silicon while the next generation of thin lm solar cells rely on rare earth metals. Dye sensitized solar cells, on the other hand, are environmentally acceptable, both in how they function, the material they use, and their manufacturing process.

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OXFORD PHOTOVOLTAIC LTD KEY DATA: FACT FILE Technology Solid state dye sensitized solar cell Established 2010 Type University spinout Location Begbroke Science Park, Oxford Employees 4 Funding VC, Business Angel, Strategic and University CEO Kevin Arthur Joined to lead the spinout process in 2010. His other founder roles at university spinouts include QuantaSol (Imperial College) and Si-Light Technologies (University of Surrey). His earlier career includes the role of VP Global Business Development at Mitel Semiconductor.

THE GRTZEL CELL The person most associated with the development of the dye sensitized solar cell is Professor Michael Grtzel of the Ecole Polytechnique Federale de Lausanne (EPFL), and because of this it is sometimes called the Grtzel Cell. The new company, Oxford Photovoltaics Ltd is commercialising the research of one of Professor Grtzels former Post-Doctoral research scientists, Dr Henry Snaith, who now holds a lectureship at the Department of Physics (Clarendon Laboratories), University of Oxford. Snaith completed his PhD at the laboratories of another leading scientist in this eld, Professor Sir Richard Friend, who heads up research into organic solar cells at the Cavendish Laboratories, Cambridge (see TTP Issue 5), and then continued his postdoctoral research at the laboratories of Professor Grtzel at the EPFL. On completing this research, he returned briey to the Cavendish, before joining the Clarendon, in October 2007, where he set up a research group to work in the area of mesoporous metal oxide electrodes and hybrid solar cells. START UP Oxford Photovoltaics Ltd was incorporated in January 2010 to commercialise the research; with the goal to achieve unsubsidised electricity generation costs that are equivalent to the Levelised Energy Cost of fossil fuels. Kevin Arthur, an entrepreneur with a track record of leading successful university spinouts, joined as Founder-CEO to lead the spin-out process, which was completed in December 2010. Conventional Dye-Sensitised Solar Cells (DSSCs) use liquidelectrolytes, which tend to be volatile, corrosive and difcult to seal, thereby severely limiting the overall performance and ease of manufacture. To overcome this researchers use a gel as a

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DYE SENSITIZED SOLAR CELLS FOR THE BUILDING INTEGRATED PHOTOVOLTAIC MARKET (CONTINUED)
semi-solid-state solution. The ideal solution however is to replace the liquid with a p-type semiconductor (a solid-state electrolyte). Among other advantages, a solid-state hole-transporter enables wide format printing of the material, thereby reducing the cost of manufacture signicantly. Oxford PVs approach is to use solid-state hole-transport materials - for example spiro-OMeTAD. Solid-state dye-sensitized solar cells (ss-DSCs) made with spiro-OMeTAD have attained efciencies of over 6%, and have exhibited good stability under elevated temperature light-soaking. Until recently it was assumed that the p-type charge transport in the organic material was much slower than n-type electron transport in the mesoporous Oxide. However, Snaith reports that his laboratories have demonstrated that the contrary is true, and as a result this strengthens the case for organic hole-transporter based ss-DSCs [see box: Hybrid Cell Approach]. COATING PROCESS Currently, Oxford PV is assessing a broad range of available coating methods to identify the most suitable for large scale manufacturing. To date, ss-DSSCs have been fabricated using spin-coating techniques to inltrate the spiro-OMeTAD. This method wastes material however and cannot scale up for larger area devices. Doctor Blading (a roll-to-roll compatible, large-area coating technique) is capable of achieving the same lling fraction as spin-coating, but uses much less material. It has been used to deposit the active layer of several types of solar cells, such as the mesoporous TiO2 layer in dye-sensitized solar cells, as well as the polymerfullerene blend, which is used in plastic solar cells. Oxford PV are now adapting their development processes to be compatible with the demands of mass production techniques, and proving that the stability of their cells is adequate for their intended BIPV application.

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SOLID-STATE DYE-SENSITIZED SOLAR CELLS The basic technology mimics the early stages of photosynthesis in plants. Light is absorbed in a dye molecule located at the junction between an n-type metal oxide and a p-type organic semiconductor. Following light absorption, photo-induced charge transfer takes place to generate free electrons, which contributes to a current in an external circuit. The original dye-sensitised solar cell used a liquid electrolyte as the p-type material. The solid-state solution being developed by Oxford offers the advantage of ease of processing and scalability.

HYBRID CELL APPROACH There is a hybrid approach where transparent n-type metal oxides are combined with p-type semiconducting polymers or small molecules. In this case, charges are only generated when light is absorbed in the polymer in close proximity to the metal oxide heterojunction. The correct meso-length scale is set by rst creating the mesostructured oxide and subsequently in-lling the pores with the polymer. However, the two main issues thought to be responsible for suboptimal operation of these solar cells are an inability effectively to inltrate semiconducting polymers into porous networks, and ineffective charge transport within the polymer phase due to non-crystalline, un-orientated polymer chains. Research at Oxford has shown that polymers can effectively penetrate porous lms with pore sizes of 20 nm and lm thickness up to 7 m. Furthermore the research has shown that hole-transport within this inltrated polymer phase is effective, resulting in well-operating dye-sensitized solar cells when combined with light absorbing dyes. Hence they believe the key is to improve the charge generation at the polymer-metal oxide interface in order to achieve the best results for this complementary hybrid approach.

Device structure

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DYE SENSITIZED SOLAR CELLS FOR THE BUILDING INTEGRATED PHOTOVOLTAIC MARKET (CONTINUED)
Key parts of the manufacturing process have been patented. Besides this it has exclusively licensed ve UK priority patent applications from the University of Oxford. There is also, as the company points out, a good deal of black art in the way the process works, which cannot be written down and simply copied. The Doctor Blade coating of the hole-transporter is one example, due to the fact that all the parameters have to be carefully controlled to obtain optimum performances. ADVANTAGES By using a printing type of coating process, Oxford PV estimates that the combined cost of materials and manufacturing can be more than 50% lower than the current lowest-cost thin lm technology. To demonstrate the manufacturing process it has installed a semi-automated screen printer at its laboratories. The company has also obtained space on the Begbroke Science Park (where the Universitys Department of Materials Science is located) in order to have access to other equipment and expertise. The company says efciency is improving steadily. Currently, DSSCs achieve around 5 to 6 % efciency, against 10 to 12 % for liquid based electro-chemical DSCs. Their advantage is that they do not need to be encased in chemically-resistant sealing, and can be directly printed via techniques which are more compatible with large scale-processing than the current lling techniques employed for electrolyte based cells. A further advantage is improved aesthetics: for example, an electro-chemical cell leaves visible lines or stripes on a transparent (usually glass) substrate due to the requirement to separate the cells physically in a module.

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BIPV MARKET The Building Integrated Photovoltaics (BIPV) market has a very good t with Oxfords strongest selling points: tunable colour, which produces a range of transparency options and therefore good operation under a wide range of light conditions. In the visible region of the spectrum, for example, absorbing light in the blue and red regions can give a green colouration, which generates the most energy for a semi-transparent solar cell. Oxford PV believes it will be possible to achieve almost complete transparency, as well as 10% efciency, by enhancing the performance and compatibility of the device with new sensitizers which only absorb light in the near IR region of the solar spectrum. This may be possible within the next ve years, says Snaith. For the time being however a target of 5% efcient bluish to green solar cell will be achievable and prove suitable for use in glazing panels and building facades.

Dr Henry Snaith

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DYE SENSITIZED SOLAR CELLS FOR THE BUILDING INTEGRATED PHOTOVOLTAIC MARKET (CONTINUED)
The total Building Integrated Photo-Voltaic market is forecast to reach over $16bn by the end of 2017 according to a report by Nano Markets. DSSCs have the advantage they can be applied directly to windows and glazing panels using screen printing which avoids complex high vacuum processes. Oxford says adding the solar cell layer to the glass glazing is a fairly trivial additional cost and provides a return in the form of electricity generated. The company is now in discussion with several major property developers, architects and construction companies. The critical issue is to meet building certication codes, as these usually require a minimum 25-year guaranteed life for materials. A high priority therefore for the company is to engage with testing and qualication experts who can validate and certify the performance of their products. WAY FORWARD The start-up funds are being applied initially on rening the manufacturing process and recruitment of key engineers. Volume manufacturing will be outsourced to third parties, but a joint venture could be considered. There are already companies supplying the BIPV market, but their solar material is based on amorphous silicon technology. Oxford PV believes that it can achieve similar efciencies to these incumbents, but at signicantly lower costs. It is therefore counting on the combination of its cost, environmental and aesthetic advantage to attract the necessary attention from the construction value chain. www.oxfordpv.com

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