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Chem Soc Rev 1 1 Chem Soc Rev 1 5 REVIEW ARTICLE 5 Design, synthesis and photophysical studies of Q1 10 dipyrromethene-based materials: insights into Q2 10 Cite this: DOI: 10.1039/c3cs60411j their incorporation in organic photovoltaic applications ab a 15 Andre´ Bessette and Garry S. Hanan* 15 This review article presents the most recent developments in the use of materials based on the dipyrromethene (DPM) dye and some of its structurally related azadipyrromethenes (ADPM) for organic photovoltaic applications (OPV). These chromophores and especially their corresponding BF2-chelated 20 derivatives BODIPY and aza-BODIPY, respectively, are well known for fluorescence-based applications 20 but are relatively new in the photovoltaic research field. This work examines the variety of relevant designs, synthetic methodologies and photophysical studies related to materials that incorporate these Received 12th November 2013 porphyrinoid-related dyes in their architecture. The main idea is to inspire readers to explore new DOI: 10.1039/c3cs60411j avenues in the design of next generation small-molecule and bulk-heterojunction solar cell (BHJSC) 25 OPV materials based on DPM chromophores. The main concepts are briefly explained, along with the 25 www.rsc.org/csr main challenges that are to be resolved in order to take full advantage of solar energy. 30 Introduction 30 At the end of 2009, Jacobson and Delucchi published in Scientific American the first plan to power 100% of the planet a De´partement de Chimie, Universite´ de Montre´al, Pavillon J.-A. Bombardier, with energy from renewable sources.1 In their plan, they 5155 Decelles Avenue, Montre´al, Que´bec, H3T-2B1, Canada. 35 E-mail: [email protected]; Fax: +1-514-343-7586; Tel: +1-514-340-5156 calculated that about 30% of the world’s continuous power 35 b Saint-Jean Photochimie Inc., 725 Trotter street, Saint-Jean-sur-Richelieu, Que´bec, needs of 11.5 TW should be produced by solar power within 20 J3B 8J8, Canada years. In the same vein, Gra¨tzel was already pointing out in a 40 Andre´ Bessette (Montre´al, Garry S. Hanan (Winnipeg, 40 Canada, 1987) received his BSc Canada, 1966) received his BSc in Chemistry (2009) from the from the University of Winnipeg Universite´ de Sherbrooke and his in 1989. He obtained his Diploˆme MSc (2012) from the Universite´ d’E´tudes Approfondies (1991) and 45 de Montre´al under the guidance PhD (1995) from the Universite´ 45 of Prof. G. S. Hanan. He is Louis Pasteur in Strasbourg, currently a PhD student in the France, under the supervision of Green Energy Group of Prof. Prof. J.-M. Lehn. He was then an G. S. Hanan, in collaboration Alexander von Humboldt fellow 50 with St-Jean Photochemicals Inc. with Prof. M. T. Reetz in 50 His research interests span a wide Germany and a post-doctoral Andre´ Bessette range of fields including Garry S. Hanan fellow with Professors V. Balzani photoactive and photovoltaic and S. Campagna in Italy. In materials, photophysics, self-assembly, organometallic chemistry 1998, he joined the faculty of the University of Waterloo and in 55 and polymeric materials. September 2002, he moved to the Universite´ de Montre´al where he is 55 currently professor of chemistry. 1 | Chem. Soc. Rev., 2013, 00,1À65 This journal is c The Royal Society of Chemistry 2013 Chem Soc Rev Review Article 1 Nature publication of 2001 that covering 0.1% of the Earth’s scientific community.13 Porphyrinoid dyes are essential chro- 1 surface with 10% efficiency solar cells would satisfy the world’s mophores in the light-harvesting process of natural photosys- energy needs for the time at which it was published.2 More tems; therefore they give good insight to researchers into how recently, Armaroli and Balzani presented the idea of an to create artificial ones based on them since many decades. The 5 electricity-powered world as a major challenge for the 21st understanding of photophysics and synthetic chemistry related 5 century3 and editorials have also pointed out a path toward to these derivatives is central to many research groups around competitiveness for solar energy.4 Additionally, the SunShot the globe. Actually, porphyrinoids have started to attract atten- program founded in 2010 by the US Department of Energy with tion lately for their incorporation in OPV devices.14–17 This an annual budget of nearly $300 million aimed to bring down renaissance is years after the very first example of organic solar 10 the cost of solar energy to 6 cents per kilowatt-hour by 2020.5 cell (OSC) was reported by Tang and Albrecht in 1975, who 10 Considering the well-documented change in climate that the incorporated chlorophyll-a as the photoactive layer between two world faces, first generation solar cells based on solid-state electrodes with a power-conversion efficiency of about junction and often made of silicon are a good start. This is 0.001%.18 especially true as they have conversion efficiencies currently This review will focus from an OPV point of view on the most 15 oscillating around 25% for crystalline Si based cells and of 28% recent developments of molecules that incorporate dipyrro- 15 for GaAs thin film cells.6 On the other hand, these cells are methenes (DPM) and some azadipyrromethenes (ADPM) in expensive and energy-intensive in their fabrication process, their structure (Fig. 1). Structurally, DPM and ADPM are half while their rigid shape limits them to specific applications.2 porphyrins and porphyrazines, respectively, but present inter- Fortunately, the field of light-harvesting materials is cur- esting advantages for OPV. In fact, their photophysical proper- 20 rently undergoing a tremendous growth and a rich variety of ties are similar to those of porphyrinoids, with many synthetic 20 other technologies are battling to emerge as ‘‘The Paramount advantages. First, they avoid the low-yield macrocyclization step One’’, the principal ones being photoelectrochemical cells and difficult purification of porphyrins, an important point to based on nanocrystalline junctions and interpenetrating net- consider for commercialization. Second, they offer abundant works, tandem cells for water cleavage by visible light, dye- leverage possibilities for fine-tuning of the photophysical prop- 25 sensitized solid heterojunctions and extremely thin absorber erties by variation of the substituents. Third, they present 25 (ETA) cells, and soft junctions and organic solar cells. In short, greater versatility of metal coordination geometries allowed we can say that this domain is in full growth. by a bidentate motif as compared to the more rigid square Back in 2009, Brabec studied the economic aspects of planar one of the parent family. This is of great interest from organic photovoltaic (OPV) devices in an interesting review.7 the perspective of developing new OPV materials taking advan- 30 He concluded that a low-cost technology like OPV could tage of the metallic center as a way to coarsely tune the 30 become competitive with other energy sources at an efficiency energetic levels. of around 7% and a lifetime of the module of 7 years. State-of- In order to give a good overview of recent advances and the-art devices’ conversion efficiencies are now at 9.1% for possibilities in this specific field of OPV, we propose here to polymer/fullerene organic solar cells in an inverted bulk- present the variety of synthetic methodologies, photophysical 35 heterojunction (BHJ) architecture by the American company studies and relevant designs based on small molecules or 35 Polyera8 and at 10.6% for tandem polymeric devices developed polymeric materials showing the most promising results by Sumitomo Chemical in collaboration with Pr Yang Yang at UCLA.8,9 The latter was a world record which was achieved only a few months after the reported efficiency of 9.8% for oligomer- 40 based (small-molecule) tandem solar cells achieved by the 40 German company Heliatek GmbH.10 The Nobel laureate Alan J. Heeger also reported recently solution-processed small- molecule BHJ solar cells with 6.7% efficiency.11 Such high conversion efficiencies are very promising for this field, espe- 45 cially as OPV have three major advantages compared with their 45 competing technologies: the flexibility of the material for coat- ing virtually everything as a thin film, the low weight of the device and the low cost of production. Many types of synthons are presently used at the industrial 50 scale in OPV, such as thiophene- and carbazole-based deriva- 50 tives.7 However, the quest for new families of molecules is wide open in order to resolve the few limitations that still hinder good conversion efficiencies on large surface area plastic solar cells, as discussed in a recent review.12 A good source of 55 inspiration for solar energy conversion are Nature’s photosyn- Fig. 1 Core structures of dipyrromethene (DPM) and azadipyrromethene 55 thetic systems which are still being investigated by the (ADPM). This journal is c The Royal Society of Chemistry 2013 Chem.Soc.Rev., 2013, 00,1À65 | 2 Review Article Chem Soc Rev 1 towards an improvement in the conversion efficiency of solar molecular architectures incorporating DPM and ADPM that will 1 cells. The review will be presented from a critical point of view be evaluated from an OPV point of view. For good reviews on in order to inspire readers to explore new avenues in the design the latter type of solar cells, interested readers should consult of next generation OPV materials based on DPM chromo- the papers published in 2009 by Gra¨tzel on recent advances in 5 phores. We will introduce a brief explanation of OPV concepts the field and in 2011 by Falaras et al. on ruthenium-based 5 along with the main challenges that are to be resolved.
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