Efficient Solar Cells based on Organic and hybrid Technology

Informazioni relative al progetto

ESCORT

ID dell’accordo di sovvenzione: 261920

Progetto chiuso

Data di avvio 1 Settembre 2010

Data di completamento 31 Agosto 2014

Finanziato da

• Specific Programme "Cooperation": Energy

Costo totale € 1 755 892,00

Contributo UE € 1 341 166,00

Coordinato da

CONSIGLIO NAZIONALE DELLE RICERCHE
Italy

Final Report Summary - ESCORT (Efficient Solar Cells based on Organic and hybrid Technology)

Executive Summary:
ESCORT (Efficient Solar Cells based on hybrid/ORganic Technology) is a joint EU-India coordinated project aimed at boosting the efficiency of Dye-Sensitized Solar Cells (DSCs) technology, by improving over the current state of the art by innovative materials and processes and a deeper knowledge of the devices operational mechanism.
DSCs are based on a wide-banc gap semiconductor oxide (typically TiO2) which is sensitized by a dye in either molecular or thin film form (the photoanode), along with a redox shuttle and a catalyst at the counter-electrode (the cathode). The project partition into work packages (WPs) reflected the coherent development of new materials for all device components, as well as a fundamental understanding of the materials dependencies and underlying photo-electro chemistry and physics in devices operational conditions.
The ESCORT project has massively investigated new dyes and thin film absorbers, leading to the publication of the new DSCs efficiency world record (13% under 1 sun) with a molecular dye. The winning strategy was the design and synthesis of a new push-pull porphyrin dye which enabled light absorption across the entire visible range, coupled to a cobalt-based redox shuttle that allowed the achievement of high open circuit voltages. Both materials are the results of intensive computational analyses and synthetic efforts within the ESCORT project, including new materials to effectively replace the use of platinum at the counter-electrode.
Along with new materials design, synthesis and photovoltaic testing, a substantial effort has been devoted to a deeper understanding of the fundamental factors underlying the high photovoltaic efficiency of specific combinations of e.g. dyes and redox shuttles, allowing the iterative design of new and more efficient materials.
The successful project outcome is also represented by the demonstration of DSCs based on new device fabrication setup, which has enabled us to prepare robust cells that meet the requirements for the standard test IEC 61646.
After the project started, organohalide lead perovskites, emerged as an extremely powerful class of absorbers materials for thin film DSCs. Part of the project tasks dealing with inorganic thin film absorbers and with fundamental modeling have thus been directed towards research in perovskite-based DSCs. This has led to a considerable knowledge of the electronic structure of organohalide lead perovskites and to the first example of hole transporter free perovskite-based DSC. Within the project duration this activity has led to the achievement of a 12.6% efficient device.
The Indian ESCORT partners have actively participated in all R&D activities, leading to 12 joint publications in international peer reviewed journal out of the total 70 project publications. A strong synergistic approach was established by consistent management and coordination activities. A very successful DSCs summer school was organized in India at project mid-term, with the participation of several students from Indian institutions and lectures given by world-class leading scientists in the DSCs field. Several bilateral exchange research visits have further fostered the joint R&D project activities, including both students and senior staff exchange. A strong return for the European industry is expected by the widespread diffusion of DSCs in India through the ESCORT project, both in terms of materials commercialization and IP exploitation.

Project Context and Objectives:
ESCORT is a joint EU-India coordinated project aimed at boosting the efficiency of Dye-Sensitized Solar Cells (DSC) technology, by improving over the current state of the art by innovative materials and processes and a deeper knowledge of the devices operational mechanism.
ESCORT involves both RTD activities (WP 1-4), management (WP5) and scientific coordination (WP6), respectively, also in relation to training and mobility between EU/India students and researchers, see Annex 1 which gathers all the Schemes, Figures and Tables.
The challenge facing the photovoltaic industry is cost effectiveness through much lower embodied energy. Plastic electronics and solution-processable inorganic semiconductors can revolutionise this industry due to their relatively easy and low cost processability (low embodied energy). The efficiency of solar cells fabricated from these “cheap” materials, is approaching competitive values, with comparison tests showing better performance for excitonic solar cells with reference to amorphous silicon in typical Northern European conditions.
The ESCORT concept is to integrate novel materials with knowledge-intensive characterization and processes to lead to viable, cost effective, solar energy. DSC, introduced by the EPFL ESCORT partner in 1991, have reached high solar to electric power conversion efficiencies, currently exceeding 11%. The operation of DSCs mimics photosynthesis in that they achieve the separation of light harvesting and charge carrier transport, thus the maximum power point is virtually independent of light level.
The critical DSC sub-systems have been developed and investigated in a coherent manner; the light absorbing dye and/or semiconductor thin film, the electron-transporting mesostructured oxide and the electrolyte/hole-transporter sub-system. Special attention has been paid to the engineering of proper coatings for prototype and large-scale DSC cells and modules, allowing light losses to be minimized. The long-term device stability (both at the lab-scale and sub-module scale size) is one of the main issues which has been addressed by our industrial partners.
By joining the top academic and industrial institutions from EU and India we have achieved a substantial success in our planned activities. The reinforcement of existing collaborations and the establishment of new channels between the EU and Indian partners has fostered bidirectional exchange and mobility of students and researchers, strongly enhancing the consciousness of the potential of DSC technology from both sides.
Using creative molecular engineering and exploiting the most recent advancements in nanomaterial technology we have already increased the DSC conversion efficiency above currently top values of 11% to realize a sustainable, stable and commercially viable prototype.
The research on light absorbing materials is addressing the major challenge in DSC, i.e. to increase the DSC photocurrent output and open circuit potential within the same material class, minimizing at the same time the light losses associated to light reflection. Thus, the ESCORT project is creating new panchromatic sensitizers based on newly designed metal complexes, developing novel routes to nanostructured architectures based on molecular self-assembly, developing enhanced redox mediator sub-systems along with minimising light losses by proper anti-reflective coatings while retaining component compatibility and consequential stability. Theoretical analyses of charge generation and recombination, necessary for understanding and improving energy conversion, and a broad range of device-physics, photo-physics and physical chemistry analytical tools are also enabling a complete development of the science associated with the technological developments, in-turn enhancing the technological advancement. The output of this basic RTD activities constitutes the input to our industrial partners, to assess the viability of large scale materials synthesis and their integration into scalable, pre-industrial, DSC devices.
The ESCORT key objectives, as included in Annex I to the Grant Agreement, are outlined below:

I. Design and synthesis of innovative dye-sensitizers with unprecedented performance, property tunability and stability.
Confer highly efficient and spectrally selective light harvesting and supramolecular hole transport properties to the ruthenium sensitizers by appropriate molecular engineering of their ligands, increasing at the same time their stability grafting onto TiO2. Pursue ligand engineering to ensure a high open circuit potential in DSC. Increase the long-term stability of ruthenium sensitizers by replacing their thiocyanate ligands.
Develop organic and metallorganic sensitizers endowed with very high molar extinction coefficients and tunable absorption from the visible into the near-IR regions. Evaluate series of homologous sensitizers in which a continuous variation of the oxidation potential allows to gauge the limiting factors for oxidized dye recombination by the electrolyte.
Evaluate possible interactions between the dyes and electrolyte components to minimize recombination.
II. Explore new concepts of photon capture by quantum dots and thin-film inorganic materials.
Evaluate and determine the forecast benefits of quantum dot technology chemically bound to the mesoscopic architecture of the charge collecting oxide semiconductor. The purpose of the quantum dot-based antenna is to provide efficient capture of near IR light and efficient charge extraction, modulated by varying their size and shape. The materials as well as their molecular and mesoscopic architecture will be judiciously selected to yield maximal power generation. Evaluate the potential of extremely thin absorbers (ETA) based on inorganic materials, such as Sb2S3 and Bi2S3 metal-chalcogenides in innovative DSC configurations, including organic hole transporters for solid-state devices.
III. Provide means for enhanced and vectorial electron transport in the mesoscopic semiconductor through chemical control of the nanostructure, with incorporation of nanorod/nanotube morphologies.

IV. Improve the stability over traditionally employed electrolytes by investigating novel transition metal complexes as standalone redox mediators which are inexpensive, transparent and redox stable. Investigate novel redox mediators based on organic redox couples to induce stable and efficient charge separation and regeneration, as alternatives to existing hole-transporting materials, which are coloured (problems with filtering) while starting from existing organic redox couples we may more easily convert them into colourless materials. These novel electrolytes are also better compatible for extremely thin absorbers based on inorganic or hybrid materials.
V. Pursue the understanding of interfaces, charge separation, electron transport and recombination through intensive computational modeling and transient spectroscopic, photoelectrochemical, and electronic analytical techniques.
Understand the processes affecting long term stability in DSC operation under different stress conditions so that the materials and structural research and development activities can be effectively directed.
VI. Develop microscopically fine structures to minimize reflection losses from the FTOcoated
glasses, by means of the moth‟s eye surface layer, in which the refractive index vary gradually from unity to that of the bulk material, reducing by up to 10% the losses of nonperpendicular incident light. Introduce self-cleaning super-hydrophobic coatings for increased DSC operational lifetime. Assess the effectiveness of both approaches in the DSC framework.

VII. Achieve commercially viable longevity via intensive and directed lifetime testing analysis and enhancement of device size cells, while remaining compatible with large area device fabrication procedures.
Develop large-area deposition techniques for metal oxide semiconductors and lowtemperature materials processing. Investigate cell degradation mechanisms in real-scale modules.

Project Results:
We published a total of 70 publications in international peer-reviewed journals, of which 12 EU-India joint publications (11 published, 1 submitted/in press), authors highlighted in bold in the list below. All publications have been provided in open access (with the exception of five publications for which an agreement with the publisher has not been achieved), thus maximizing the project outcome dissemination.
List of publications:

1. Swami, S.J.; Chaturvedi, N.; Kumar, A.; Kapoor, R.; Dutta, V.; Frey, J.; Moehl, T.; Gräetzel, M.; Mathew, S.; Nazeeruddin, M. K. “Investigation of electrodeposited cobalt sulphide counter electrodes and their application in next-generation dye sensitized solar cells featuring organic dyes and cobalt-based redox electrolytes” J. Power Sources, submitted.

2. Grisorio R., Agosta R., De Marco L., Iacobellis R., Suranna G.P. Manca M., Mastrorilli P., Gigli G. “Enhancing dye-sensitized solar cell performances by small structural modification: toward highly efficient π extended organic sensitizers” ChemSusChem 2014, 7, 2659–2669. (link)

3. Salvatori, P.; Agrawal, S.; Barreddi, C.; Chandrasekharam, M.; de Borniol, M.; De Angelis, F. "Stability of ruthenium/organic dye co-sensitized solar cells: a joint experimental and computational investigation" RSC Advances 2014, DOI: 10.1039/C4RA09472G. (link)

4. Gupta, K. S. V. Zhang, J.; Marotta, G.; Reddy, M. A.; Singh, S. P.; Islam, A.; Han, L.; De Angelis, F.; Chandrasekharam, M.; Pastore, M. "Effect of the anchoring group in the performance of carbazole-phenothiazine dyads for dye-sensitized solar cells" Dyes and Pigments 2014, 113, 536-545. (link)

5. De Gregorio, G.L.; Giannuzzi, R.; Cipolla, M.P.; Agosta, R.; Capodilupo, A.; Gigli, G.; Manca M. “Iodopropyl-branched polysiloxane gel electrolytes with improved ionic conductivity upon cross-linking” Chem. Commun. 2014, 50, 13904-13906. (link)

6. Sudhakar, K.; Giribabu, L.; Salvatori, P.; De Angelis, F. "Triphenylamine-functionalized corrole sensitizers for solar-cell applications" Phys. Status Solidi 2014, DOI10.1002/pssa.201431169. (link)

7. Manca, M.; De Marco, L.; Giannuzzi, R.; Agosta, R.; Dwivedi, C.; Qualtieri, A.; Dutta, V.; Gigli, G. "TiO2 nanorod-based photoelectrodes for dye solar cells with tunable morphological features" Thin Solid Films 2014, 568, 122–130. (link)

8. Vaissier, V.; Mosconi, E.; Moia, D.; Pastore, M.; Frost, J. M.; De Angelis, F.; Barnes, P. R. F.; Nelson, J. "Effect of Molecular Fluctuations on Hole Diffusion within Dye Monolayers" Chem. Mater. 2014, 26, 4731–4740. (link)

9. Gottesman, R.; Haltzi, E.; Gouda, L.; Tirosh, S.; Boudhana,Y; Zaban, A.; Mosconi, E.; De Angelis, F. “Extremely slow photoconductivity response of CH3NH3PbI3 Perovskites Suggesting Structural Changes under working conditions” J. Phys. Chem. Lett. 2014, 5, 2662-2669. (link)

10. Manca, M.; Beke, S.; De Marco, L.; Pareo, P.; Qualtieri, A.; Cannavale, A.; Brandi, F.; Gigli, G. “A 3D Photoelectrode for Dye Solar Cells Realized by Laser Micromachining of Photosensitive Glass" J. Phys. Chem. C 2014, 118, 17100–17107. (link)

11. Agosta, R.; Grisorio, R.; De Marco, L.; Iacobellis, R.; Suranna, G.P.; Mastrorilli, P.; Gigli, G.; Manca, M. “An engineered co-sensitization system for highly” Chem Commun. 2014, 50, 9451 (link)

12. De Angelis, F.; Di Valentin, C.; Fantacci, S.; Vittadini, A.; Selloni, A. "Theoretical Studies on Anatase and Less Common TiO2 Phases: Bulk, Surfaces, and Nanomaterials" Chem. Rev. 2014, 114, 9708–9753. (link)

13. De Angelis, F. "Modeling Materials and Processes in Hybrid/Organic Photovoltaics: From Dye-Sensitized to Perovskite Solar Cells" Acc. Chem. Res. 2014, DOI: 10.1021/ar500089n. (link)

14. Lobello, M. G.; De Angelis, F.; Fantacci, S. "A computational approach to the electronic, optical and acid-base properties of Ru(II) dyes for photoelectrochemical solar cells applications" Polyhedron 2014, 82, 88-103. (link)

15. Azpiroz, J. M.; De Angelis, F. "DFT/TDDFT Study of the Adsorption of N3 and N719 Dyes on ZnO(1010)Surfaces" J. Phys. Chem. A 2014, 118, 5885–5893. (link)

16. Bai, Y.; Mora-Seró, I.; De Angelis, F.; Bisquert, J.; Wang, P. "Titanium Dioxide Nanomaterials for Photovoltaic Applications" Chem. Rev. 2014, 114, 10095–10130. (link)

17. Ronca, E.; De Angelis, F.; Fantacci, S. "TDDFT Modeling of Spin-Orbit Coupling in Ruthenium and Osmium Solar Cell Sensitizers" J. Phys. Chem. C 2014,118, 17067–17078. (link)

18. Ronca, E.; Marotta, G.; Pastore, M.; De Angelis, F. "Effect of Sensitizer Structure and TiO2 Protonation on Charge Generation in Dye-Sensitized Solar Cells" J. Phys. Chem. C 2014, 118, 16927–16940. (link)

19. Roiati, V.; Mosconi, E.; Listorti, A.; Colella, S.; Gigli, G.; De Angelis F. "Stark Effect in Perovskite/TiO2 Solar Cells: Evidence of Local Interfacial Order" Nano Lett. 2014, 14, 2168–2174. (link)

20. Mathew, S.; Yella, A.; Gao, P.; Humphry-Baker, R.; Curchod, B.F.E.; Ashari-Astani, N.; Tavernelli, I.; Rothlisberger, U.; Nazeeruddin, M. K.; Grätzel, M."Dye-sensitized solar cells with 13% efficiency achieved through the molecular engineering of porphyrin sensitizers" Nat. Chem. 2014, 6, 242–247. (link)

21. Nunzi, F.; Storchi, L.; Manca, M.; Giannuzzi, M.; Gigli, G.; De Angelis, F. "Shape and Morphology Effects on the Electronic Structure of TiO2 Nanostructures: From Nanocrystals to Nanorods" ACS Appl. Mater. Interfaces 2014, 6, 2471–2478. (link)

22. Ronca, E.; Pastore, M.; Belpassi, L.; De Angelis, F.; Angeli, C.; Cimiraglia, R.; Tarantelli, F. "Charge-displacement analysis for excited states" J. Chem. Phys. 2014, 140, 054110 (link)

23. Calbo, J.; Pastore, M.; Mosconi, E.; Ortí, E.; De Angelis, F. "Computational modeling of single- versus double-anchoring modes in di-branched organic sensitizers on TiO2 surfaces: structural and electronic properties" Phys. Chem. Chem. Phys. 2014, 16, 4709-4719. (link)

24. Azpiroz, J. M.; Mosconi, E.; Ugalde, J. M.; De Angelis, F. " Effect of Structural Dynamics on the Opto-Electronic Properties of Bare and Hydrated ZnS QDs " J. Phys. Chem. C 2014, 118, 3274–3284. (link)

25. Marotta, G.; Lobello, M. G.; Anselmi, C.; Barozzino Consiglio, G.; Calamante, M.; Mordini, A.; Pastore, M.; De Angelis, F. "An Integrated Experimental and Theoretical Approach to the Spectroscopy of Organic-Dye-Sensitized TiO2 Heterointerfaces: Disentangling the Effects of Aggregation, Solvation, and Surface Protonation" ChemPhysChem 2014, 15, 1116–1125. (link)

26. Salvatori, P.; Amat, A.; Pastore, M.; Vitillaro, G.; Sudhakar, K.; Giribabu, L.; Soujanya, Y.; De Angelis, F. "Corrole Dyes for Dye-Sensitized Solar Cells: the Crucial Role of the Dye/Semiconductor Energy Level Alignment" Comp. Theor. Chem 2014, 1030, 59–66. (link)

27. Fantacci, S.; Ronca, E.; De Angelis, F."Impact of Spin–Orbit Coupling on Photocurrent Generation in Ruthenium Dye-Sensitized Solar Cells" J. Phys. Chem. Lett. 2014, 5, 375–380. (link)

28. Lobello, M. G.; Wu, K. K.; Marri, A. R.; Marotta, G.; Gratzel, M.; Nazeeruddin, M. K.; Chi, Y.; Malapaka, C.; Vitillaro, G.; De Angelis, F. " Engineering of Ru(II) dyes for interfacial and light-harvesting optimization " Dalton Trans. 2014, 43, 2726-2732. (link)

29. Pastore, M.; Selloni, A.; Fantacci, S.; De Angelis, F. "Electronic and Optical Properties of Dye-Sensitized TiO2 Interfaces" Top. Curr. Chem. 2014, 352, 1- 45. (link)

30. Marotta, G.; Anil Reddy, M.; Singh, S. P.; Islam, A.; Han, L.; De Angelis, F.; Pastore, M.; Chandrasekharam, M. "Novel Carbazole-Phenothiazine Dyads for Dye-Sensitized Solar Cells: a Combined Experimental and Theoretical Study" ACS Appl. Mater. Interfaces 2013, 5, 9635–9647. (link)

31. Gao, P.; Kim, Y.J.; Yum, J.H.; Holcombe, T.W.; Nazeeruddin, M. K.; Graetzel, M. “Facile synthesis of a bulky BPTPA donor group suitable for cobalt electrolyte based dye sensitized solar cells” J. Mater. Chem. A 2013, 1, 5535-5544. (link)

32. Dragonetti, C.; Colombo, A.; Magni, M.; Mussini, P.; Nisic, F.; Roberto, D.; Ugo, R.; Valore, A.; Valsecchi, A.; Salvatori, P.; Lobello, M. G.; De Angelis, F. "Thiocyanate-Free Ruthenium(II) Sensitizer with a Pyrid-2-yltetrazolate Ligand for Dye-Sensitized Solar Cells" Inorg. Chem. 2013, 52, 10723–10725. (link)

33. De Marco, L.; Di Carlo, G.; Giannuzzi, R.; Manca, M.; Riccucci, C.; Ingo, G. M.; Gigli, G. "Highly efficient photoanodes for dye solar cells with a hierarchical meso-ordered structure" Phys. Chem. Chem. Phys. 2013, 15, 16949-16955. (link)

34. Lobello, M.; Fantacci, S.; Manfredi, N.; Coluccini, C.; Abbotto, A.; Nazeeruddin, M. K.; De Angelis, F. "Design of Ru(II) sensitizers endowed by three anchoring units for adsorption mode and light harvesting optimization" Thin Solid Films 2013, 560, 86–93. (link)

35. Barolo, C.; Yum, J.-H.; Artuso, E.; Barbero, N.; Di Censo, D.; Lobello, M. G.; Fantacci, S.; De Angelis, F.; Graetzel, M.; Nazeeruddin, M. K.; Viscardi, G. "A Simple Synthetic Route to Obtain Pure Trans-Ruthenium(II) Complexes for Dye-Sensitized Solar Cell Applications" ChemSusChem 2013, 6, 2170–2180. (link)

36. Singh, V. K.; Salvatori, P.; Amat, A.; Agrawal, S.; De Angelis, F.; Nazeeruddin, M. K.; Krishna, N. V.; Giribabu, L. "Near-infrared absorbing unsymmetrical Zn(II) phthalocyanine for dye-sensitized solar cells" Inorg. Chim. Acta 2013, 407, 289–296. (link)

37. De Marco, L.; Manca, M.; Giannuzzi, R.; Belviso, M. R.; Cozzoli, P. D.; Gigli, G. "Shape-tailored TiO2 nanocrystals with synergic peculiarities as building blocks for highly efficient multi-stack dye solar cells" Energy Environ. Sci. 2013, 6, 1791-1795. (link)

38. Loiudice, A.; Rizzo, A.; Grancini, G.; Biasiucci, M.; Belviso, M. R.; Corricelli, M.; Curri, M. L.; Striccoli, M.; Agostiano, A.; Cozzoli, P. D.; Petrozza, A.; Lanzani, G.; Gigli, G. "Fabrication of flexible all-inorganic nanocrystal solar cells by room-temperature processing" Energy Environ. Sci. 2013, 6, 1565–1572. (link)

39. Giansante, C.; Carbone, L.; Giannini, C.; Altamura, D.; Ameer, Z.; Maruccio, G.; Loiudice, A.; Belviso, M. R.; Cozzoli, P. D.; Rizzo, A.; Gigli, G. "Colloidal Arenethiolate-Capped PbS Quantum Dots: Optoelectronic Properties, Self-Assembly, and Application in Solution-Cast Photovoltaics" J. Phys. Chem. C 2013, 117, 13305–13317. (link)

40. Salvatori, P.; Marotta, G.; Cinti, A.; Mosconi, E.; Panigrahi, M.; Giribabu, L.; Nazeeruddin, M. K.; De Angelis, F. "A New Terpyridine Cobalt Complex Redox Shuttle for Dye-Sensitized Solar Cells" Inorg. Chim. Acta 2013, 406, 106–112. (link)

41. Mosconi, E.; Amat, A.; Nazeeruddin, M. K.; Graetzel, M.; De Angelis, F "First Principles Modeling of Mixed Halide Organometal Perovskites for Photovoltaic Applications" J. Phys. Chem. C 2013, 117, 13902–13913. (link)

42. Agrawal, S.; Pastore, M.; Marotta, G.; Reddy, M. A.; Chandrasekharam, M.; De Angelis, F. "Optical Properties and Aggregation of Phenothiazinebased Dye Sensitisers for Solar Cells Applications: A Combined Experimental and Computational Investigation" J. Phys. Chem. C 2013, 117, 9613–9622 (link)

43. Giribabu, L.; Singh, V.K.; Jella, T.; Soujanya, Y.; Amat, A.; De Angelis, F.; Yella, A.; Gao, P.; Nazeeruddin, M. K. "Sterically demanded unsymmetrical zinc phthalocyanines for dye-sensitized solar cells" Dyes Pigments 2013, 98, 518–529 (link)

44. Wang, S. W.; Wu, K. L.; Ghadiri, E.; Lobello, M. G.; Ho, Y. C.; Chi, Y.; Moser, J. E.; De Angelis, F.; Graetzel, M.; Nazeeruddin, M. K. "Engineering of Thiocyanate-free Ru(II) Sensitizers for High Efficiency Dye-Sensitized Solar Cells" Chem. Sci. 2013, 4, 2423-2433 (link)

45. Fantacci, S.; Lobello, M.G.; De Angelis, F. "Everything you always wanted to Know about Black Dye (but Were Afraid to Ask): A DFT/TDDFT Investigation" Chimia 2013, 67, 121–128. (link)

46. Pastore, M.; De Angelis, F. "Intermolecular Interactions in Dye-Sensitized Solar Cells: A Computational Modeling Perspective" J. Phys. Chem. Lett. 2013, 4, 956–974. (link)

47. Salvatori, P.; Marotta, G.; Cinti, A.; Anselmi, C.; Mosconi, E.; De Angelis, F. "Supramolecular Interactions of Chenodeoxycholic Acid Increase the Efficiency of Dye-Sensitized Solar Cells Based on a Cobalt Electrolyte" J. Phys. Chem. C 2013, 117, 3874–3887. (link)

48. Ronca, E.; Pastore, M.; Belpassi, L.; Tarantelli, F.; De Angelis, F. "Influence of the Dye Molecular Structure on the TiO2 Conduction Band in Dye-Sensitized Solar Cells: Disentangling Charge Transfer and Electrostatic Effects" Energy Environ. Sci. 2013, 6, 183-193. (link)

49. Agosta, R.; Giannuzzi, R.; De Marco, L.; Manca, M.; Belviso, M.; Cozzoli, P. D.; Gigli, G. "Electrochemical Assessment of the Band-Edge Positioning in Shape-Tailored TiO2-Nanorods-Based Photoelectrodes for Dye Solar Cells" J. Phys. Chem. C 2013, 117, 2574–2583. (link)

50. Loiudice, A.; Rizzo, A.; Biasiucci, M.; Gigli, G. “Bulk Heterojunction versus Diffused Bilayer: The Role of Device Geometry in Solution p-Doped Polymer-Based Solar Cells" J. Phys. Chem. Lett. 2012, 3, 1908-1915. (link)

51. Mastria, R.; Rizzo, A.; Nobile, C.; Kumar, S.; Maruccio, G.; Gigli, G. “Improved photovoltaic performances by post-deposition acidic treatments on tetrapod shaped colloidal nanocrystal solids” Nanotechnology 2012, 23, 305403. (link)

52. Etgar, L.; Gao, P.; Xue, Z.; Peng, Q.; Chandiran, A. K., Liu, B.; Nazeeruddin, M. K.; Graetzel, M. "Mesoscopic CH3NH3PbI3/TiO2 Heterojunction Solar Cells" J. Am. Chem. Soc. 2012, 134, 17396-17399. (link)

53. Mosconi, E.; Yum, J. H.; Kessler, F.; Gomez-Garcia, C. J.; Zuccaccia, C.; Cinti, A.; Nazeeruddin, M. K.; Graetzel, M.; De Angelis, F. "Cobalt Electrolyte/Dye Interactions in Dye-Sensitized Solar Cells: A combined Computational and Experimental Study" J. Am. Chem. Soc. 2012, 134, 19438-19453. (link)

54. Anselmi, C.; Mosconi, E.; Pastore, M.; Ronca, E.; De Angelis, F. "Adsorption of organic dyes on TiO2 surfaces in dye-sensitized solar cells: interplay of theory and experiment " Phys. Chem. Chem. Phys. 2012, 14, 15963-15974. (link)

55. Gao, Peng; Tsao, H. N.; Graetzel, M.; Nazeeruddin, M. K. "Fine-tuning the Electronic Structure of Organic Dyes for Dye-Sensitized Solar Cells" Org. Lett. 2012, 14, 4330–4333. (link)

56. Coluccini, C.; Manfredi, N.; Salamone, M. M.; Ruffo, R.; Lobello, M. G.; De Angelis, F.; Abbotto, A. “Quaterpyridine ligands for panchromatic Ru(II) dye sensitizers” J. Org. Chem. 2012, 77, 7945–7956. (link)

57. Pizzoli, G.; Lobello , M. G.; Carlotti, B.; Elisei, F.; Nazeeruddin, M. K.; Vitillaro, G.; De Angelis, F. “Acid–base properties of the N3 ruthenium(II) solar cell sensitizer: a combined experimental and computational analysis” Dalton Trans. 2012, 41, 11841–11848. (link)

58. Loiudice, A.; Rizzo, A.; Latini, G:; Nobile, C.; de Giorgi, M.; Gigli, G. “Graded vertical phase separation of donor/acceptor species for polymer rsolar cells" Solar Energy Materials & Solar Cells 2012, 100, 147-152. (link)

59. Grancini, G.; Biasiucci, M.; Mastria, R.; Scotognella, F.; Tassone, F.; Polli, D.; Gigli, G.; Lanzani, G. “Dynamic Microscopy Study of Ultrafast Charge Transfer in a Hybrid P3HT/Hyperbranched CdSe Nanoparticle Blend for Photovoltaics” J. Phys. Chem. Lett. 2012, 3, 517–523. (link)

60. Amat, A.; De Angelis, F. "Challenges in the Simulation of Dye-Sensitized ZnO Solar Cells: Quantum Confinement, Alignment of Energy Levels and Excited States Nature at the Dye/Semiconductor Interface" Phys. Chem. Chem. Phys. 2012, 14, 10662-10668. (link)

61. Kovyrshin, A.; De Angelis, F.; Neugebauer, J. "Selective TDDFT with automatic removal of ghost transitions: application to a perylene-dye-sensitized solar cell model" Phys. Chem. Chem. Phys. 2012, 14, 8608-8619. (link)

62. Mosconi, E.; Selloni, A.; De Angelis, F. "Solvent Effects on the Adsorption Geometry and Electronic Structure of Dye-Sensitized TiO2: A First-Principles Investigation" J. Phys. Chem. C 2012, 116, 5932–5940. (link)

63. Ahmad, S.; Dellorto, E.; Yum, J. H.; Kessler, F.; Nazeeruddin, M. K.; Graetzel, M. "Towards flexibility: Metal free plastic cathodes for Dye sensitized solar cells" Chem. Commun. 2012, 48, 9714-9716. (link)

64. Ahmad, S.; Bessho,T.; Kessler, F.; Baranoff, E.; Frey, J.; Yi , C.; Graetzel, M.; Nazeeruddin, M. K. "A new generation of platinum and iodine free efficient dye-sensitized solar cells" Phys. Chem. Chem. Phys. 2012, 14, 10631-10639. (link)

65. Giannuzzi, R.; Manca, M.; Gigli, G. "A new electrical model for the analysis of a partially shaded dye-sensitized solar cells module" Prog. Photovolt: Res. Appl. 2012, 21, 1520–1530. (link)

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The main results, divided by WP, are summarized below:
WP1 - Dye sensitizers. The work is divided into three tasks, involving computational modelling, synthesis and testing of new dyes.
D1.1 - According to tasks I, II and III the EPFL and CNR teams have reported in the synthesis and the experimental and computational investigation of the photophysical and electrochemical properties of a number of representative unsubstituted and alkyl and (hetero)aromatic substituted quaterpyridines ligands (1a, 2a, 3a, 4a, 5a, 6a) and of the related ruthenium complexes (1d, 2d, 3d, 5d, 6d). Substituted quaterpyridines can play a crucial role in the fabrication of efficient dye-sensitized solar cells by virtue of the unique panchromatic properties, ranging from UV-Vis to NIR, of their metal complexes. Unfortunately, the difficult synthetic access (low yields, restricted quantities, low reproducibility) and the use of toxic organotin reagents of the so far reported Stille cross-coupling synthetic access has greatly limited this important potential. We have described a general synthetic access to carboxylated quaterpyridine ligands, via the Suzuki-Miyaura cross-coupling reaction. The limited stability and applicability of 2-pyridyl boronic acid and esters, which has impeded so far the application of the Suzuki coupling to the synthesis of polypyridines, has been bypassed by using stable 2-pyridyl MIDA derivatives, which were successfully coupled to a dichloro bpy intermediate readily affording a number of qpys in very satisfactory yields. Not only does this access make use of non-toxic boronic derivatives, but we have shown that the scope is general and can be systematically applied to the synthesis of variously substituted polypyridines. In order to demonstrate the potential of these ligands to the synthesis of complexes, we also describe the preparation of the corresponding bis-thiocyanato Ru(II) complexes through an efficient microwave-assisted route which bypasses the use of time- and product-consuming Sephadex column chromatography, as commonly done for most Ru(II) dyes. Finally, to evaluate their properties, the complexes 1d, 3d and 6d have been used as sensitizer in DSC devices.
A highest photocurrent of 19.8 mA/cm2 with a global efficiency of 6.9 % was achieved for DSCs based on complex 6d co-sensitized with the D35 organic dye, Figure 1A, thus closely meeting the requirements of this deliverables and of the corresponding milestone (MS1).
D1.2 - The joint EU-India team (EPFL, CNR and IICT) designed, synthesized, characterized and tested in DSC devices three classes of sensitizers, listed below:
1. Ruthenium complexes (in collaboration with IICT, India);
2. Organic sensitizers (in collaboration with IICT, India);
3. Metallorganic porphyrins, phtalocyanine and corroles (in collaboration with IICT, India).
The three investigated dye classes are representative of the most performing state of the art dyes, which were thoroughly investigated for a comparative search of the “perfect dye”. Although the focus of this deliverable was mainly on ruthenium dyes, 1, based on encouraging results for classes 2 and 3, we have expanded the scope of the project by investigating these two additional classes of dyes.
Ruthenium dyes are indeed the traditional prototypical sensitizers for solar cells applications. Organic dyes are however endowed with particularly tunable optical properties and environmental advantages, coupled to favorable scale-up synthetic procedures; and metallorganic porphyrins are characterized by a high molar extinction coefficient and with intense absorptions down to ca. 750 nm, making these systems perfectly suited for standalone TiO2 sensitization or co-sensitization with organic dyes showing complementary absorptions.
High photovoltaic efficiency (above 7%) were obtained for all the three classes of dyes, achieving an impressive 13.5 % efficiency for devices fabricated with the metallorganic porphyrins, Figure 2, thus meeting the requirements of this deliverables and of the corresponding milestone (MS2).
D1.3 - The EPFL and CNR teams have reported the design, synthesis, characterization of two types of new NCS-free dyes, based on novel cyclomatelated ligands. The major advance stemming from this investigation is that ruthenium complexes are shown for the first time to achieve high efficiency (10.03 %) in conjunction to cobalt electrolytes, Figure 1D and 1E, very close to the 10.5% deliverable target.
The joint theoretical and experimental study allows us to trace some trends for the performance of the investigated series of dyes. On the basis of the theoretical analysis we showed that the NCS groups constitute binding sites for the cobalt electrolytes. We thus notice that the NCS-free dyes have the double advantage of avoiding the dye/cobalt interaction, which are responsible of the low performance in standard dyes and enhance the device stability at the same time. These two points, coupled to the non-corrosivity of cobalt-based electrolytes, opens the way to high efficiency and long durable DSC devices.
In addition to what due for the reports of D1.1 D1.2 and D1.3 a large series of new dyes synthesized by IICT-India (corroles and phtalocyanines) were computationally investigated by CNR and their photovoltaic properties was assessed by CNR and EPFL.
D1.4. - In deliverable D1.4 we summarized the main results obtained by the joint EU-India team in the design, synthesis, characterization and devices testing of new sensitizers for Dye-sensitized Solar Cells (DSCs). In particular four class of dyes, both metallorganic or fully organic, have been developed:
• Carbazole based organic sensitizers;
• Corrole dyes;
• Heteroleptic bipyridyl ruthenium dyes;
• Terpyridyl ruthenium dyes.
Carbazole based organic sensitizers. Two push-pull derivatives CAR-THIOHX and CAR-TPA, employing carbazole and triphenylamine as donor moieties, have been designed and synthesized by simple organic transformations. Photophysical and electrochemical studies revealed the potentiality of these two systems in DSCs. Under standard irradiation conditions, CAR-TPA and CAR-THIOHX exhibited 2.12 and 1.83 % of overall power conversion efficiencies respectively. The moderate photovoltaic efficiency of the sensitizers has been attributed to the poor light absorption of the sensitizers in the visible region. Density functional theory (DFT) calculations have shown a strong intramolecular charge transfer character, with the HOMOs of both the sensitizers exclusively localized on the corresponding donor moieties and LUMOs on the cyanoacrylic acid acceptor. On the other hand, it has been calculated a high dihedral angle between the carbazole donor and the phenyl bridge for these sensitizers, leading to impede the conjugation along the dyes backbone, and thus to less extended and intense absorption spectra in the visible region. Although the moderate photovoltaic efficiencies obtained, these two-donor carbazole-based dyes can be considered a promising class of sensitizers, underlining once again the key importance of the selection of optimized π-bridge moieties for organic dyes.
Corroles dyes. A series of four β-carboxy-corroles, both in free-base and in copper complexes form have been investigated. We find that the extended conjugation along the acceptor carboxylic units, although it is not favored for steric reasons, lead to a band gap reduction. A detailed comparison between calculated and experimental properties was then reported. The adsorption of two representative corrole dyes on a TiO2 cluster was also investigated to shed light on the adsorption geometry and the charge injection process into the TiO2 conduction band, finding an unfavorable level alignment between the dyes LUMO/LUMO+1 and the TiO2 conduction band. An inefficient charge injection process is thought to be the main reason for the low measured photocurrents, combined to a possibly favored back electron transfer from the TiO2 to the oxidized dye or to the electrolyte. This study demonstrates the crucial role of high-level computational modeling in the deep understanding of the chemical and physical processes occurring at the complex dye/semiconductor interfaces, allowing for a smart and efficient molecular engineering.
We also have reported a new series of corrole-based sensitizers with triphenylamine moiety with alkoxy groups at –meso position, and anchoring carboxyl group at pyrrole - position of corrole macrocycle. This structural design has the aim to improve the intramolecular charge separation, and then to enhance the photovoltaic conversion efficiencies. Unfortunately, photovoltaic studies, carried out by using in combination with a I-/I3- based electrolyte, have shown poor devices performance, in particular for the copper complexes, even if slight improvements with respect to the reference structures were obtained and the measured short-circuit photocurrents followed the trend in optical absorption spectra. Computational investigation on dyes, both in solution and anchored on a TiO2 cluster surface, has suggested as possible reasons for the low photovoltaic performances the poor TiO2 sensitization and an unfavorable electron injection process, due to an incorrect energy level alignment between the dye LUMO and the semiconductor conduction band states.
Heteroleptic bipyridyl ruthenium dyes. We have reported the synthesis of six novel Ru(II) complexes to be used as DSC sensitizers. Five of these are symmetrical heteroleptic dyes, while the last one, a dissymmetrical one, was designed in order to investigate the three-anchoring approach, possibly leading to improved interfacial properties and to better stability and power conversion efficiency. These complexes have shown promising optical and electronic properties, leading to overall efficiencies comparable to the reference N719 dye, approaching 8%, when used in combination with a liquid iodine-based electrolyte and chenodeoxycholic acid as coadsorbent. In particular, the use of long alkyl chains in the molecular structure, able to reduce the parasitic recombination processes allowed to achieve remarkably high photovoltages. On the other hand, the dissymmetric complex, for the three-anchoring design concept, showed lower performances, probably due to the competition between different binding modes, leading to an unfavorable dye coverage on the TiO2 surface and to a less efficient electron injection process.
Terpyridyl ruthenium dyes. Terpyridyl ruthenium dyes have been synthesized by the Indian partners. In particular, the dyes MC124, 125 and 127 the research group of Dr. M. Chandrasekharam, IICT, while the dyes SPS-GS-1, 2,have been synthesized by theresearchgroup of Dr.S. P. Singh, IICT. The main problems of these complexes are about the solubility. In fact MC124 dye exhibits low solubility in the DMF/EtOH mixture and the poor performances of this complex could be due to such problem. Also MC120, MC121 and MC123 complexes has low solubility in DMF/EtOH (however better than MC124) but in this case the PV performances were not affected by such problem. MC118, MC122, MC125 and MC127 are solubles in DMF/EtOH mixture. For MC126 a different solvent mixture were employed (experimental details section). The bad performances of the devices realized with MC125 and MC127 could be due to dye loading issue or limitations in light absorption by sensitized photoanodes.
In order to increase the photocurrent density of the working devices, some modifications to device fabrication procedure and employed materials will be done:
1. Use of thicker TiO2 layer in order to increase the dye load (12μ of transp. TiO2 + 4μ of scattering layer).
2. Increase of the sensitization time (20 h) with anti-aggregant (CDCA or DINHOP) added to sensitization solution.
3. Use of different solvent mixture in order to solve the solubility problem.
The investigation of the structure-efficiency relationship in these new classes of sensitizers allowed us to individuate the guidelines to design more efficient compounds with optimized photoelectrochemical properties. The deliverable 1.4 demonstrated the crucial role of the combined theoretical-experimental and device data in the deep understanding of the chemical and physical processes occurring in an operating DSC device. This will allow for a smart and efficient molecular engineering of compounds with tailored properties in order to improve the conversion efficiencies of the solar cells.
In addition to the work reported on deliverable D1.4 we have reported the synthesis, photovoltaic characterization and computational modelling of two novel carbazole-phenothiazine dyes with malonic (CSORG2) and carboxylic (CSORG3) acid as anchoring units. An improvement of the photovoltaic performances is observed when the malonic acid is employed in place of the carboxylic acid, even if the highest efficiencies for this family of organic dyes were recorded with the use of the cyanoacrylic and rhodanine-3-aceti acid as anchoring units. The low photocurrents measured in the case of the carboxylic anchoring are rationalized on the basis of the computational modelling of the isolated dye in solution as well as the investigation of the electronic structure of extended dye-sensitized TiO2 models. The theoretical calculations suggest that the low short current densities might arise from the unfavourable interplay of the dye’s optical properties (blue shift of the absorption spectrum) and of the energy alignment between the dye’s LUMO and the semiconductor conduction band edge, possibly causing an inefficient electron injection process.

WP2 - Metal oxide/Coatings. The work is organized into three tasks, involving the synthesis of nanostructured oxides as photoanodes, the preparation of anti-reflective / self-cleaning coatings and their testing in DSCs.

D2.1 - The performance of solar energy conversion devices employing mesoscopic photoelectrodes depends critically on their nanostructure. This is particularly evident for DSCs, where charge percolation through the TiO2 electrodes takes up to milliseconds. Slow charge extraction increases the chances of electron-hole recombination at the mesoporous TiO2 - electrolyte interface, and thus limits DSCs to be used with only a few electrolytes that offer low recombination rates. This promoted intensive research toward photoanodes comprising nanoporous materials characterized by enhanced electron transport properties due to the features of highly decreased intercrystalline contacts and stretched grown structure with specified directionality. Here IIT-It demonstrated a general approach by which colloidal anatase TiO2 nanocrystals with anisotropically tailored linear and branched shapes can be safely processed into high-quality mesoporous DSCs photoelectrodes. The performances of the devices based on TiO2 nanorods produced in the framework of the ESCORT program largely overcome those achieved by conventional, commercially available TiO2 nanoparticles, measured under the same test conditions. A highest performance of 10.7% is obtained by employing DSCs photoanodes based on specifically tailored combinations of TiO2 nanorods of varying aspect ratio, Figure 3.
The concurrent development of high-performance materials, new device and system architectures and nanofabrication processes has driven widespread research and development in the field of nanostructures for photon management in photovoltaics. The fundamental goals of photon management are to reduce incident light reflection, improve absorption, and tailor the optical properties of a device for use in different types of energy conversion systems. Nanostructures rely on a core set of phenomena to attain these goals, including gradation of the refractive index, coupling to waveguide modes through surface structuring, and modification of the photonic band structure of a device.
D2.2 -. In deliverable D2.2 we have shown the successful implementation of hole-conductor free solid state DSSCs based on inorganic perovskite absorbers, with top efficiency exceeding the target 5% benchmark. Optimization of the same material processing with an organic hole conductor, carried out in collaboration with IIT-India, led to a photovoltaic efficiency of 12.6%, Figure 4, one of the highest values obtained with perovskites inorganic absorbers. Further tests were conducted, again in collaboration with IIT-India, on solid state DSSCs based on Continuous Spray pyrolysis (CoSp) synthesized TiO2 nanoparticles, which together with a perovskite absorber led to 5.93% efficiency. Finally, alternative inorganic materials for DSSC counterelectrodes were tested, leading to comparable efficiency to those obtained with conventional Pt-based materials. Our results exceed the target efficiency of this deliverable by a factor 2.5 highlighting the enormous potential of perovskite inorganic absorbers for solid state DSSCs.
Milestone 6 (MS6), which deals with the fabrication of DSC based on inorganic absorbers with 5% efficiency, has been successfully achieved.
D2.3 – IIT-It reported on the achievement of high quality superhydrophobic / antireflective coatings to use in DSSCs. A cost-effective fabrication method based on the use of sol–gel coatings has been set up, which has allowed us to produce high–quality, broad–band anti-reflecting coatings with excellent optical and mechanical properties. A high transmittance of 99.1 i.e. only 0.9% loss compared to full transmittance, was recorded at 525 nm, which led to an 8% transmittance enhancement compared to a bare glass. A second strategic issue in the development of functional coatings concerns the realization of robust transparent coatings which are capable to impart a “self-cleaning” or an “easy-to-clean” effect to the front end glass of a DSC in the perspective of reducing or eliminating the impact of façade cleaning in the next generation of building-integrated DSSC modules. An increase of more than 3% in transmission within all of the visible range and a highest absolute transmittance of 93.6% at 500 nm were observed.
Finally, the fabricated anti-reflective coatings have been employed in conjunction to DSSC fabricated from a multi-layered photoelectrode delivering a 5% photocurrent increase and an overall 3.3% efficiency increase, Figure 5. These results closely match and in some instance surpass, the targets of <5% losses established by MS5. A sample of the coatings will be tested by the Dyesol partner to assess its industrial viability.
In collaboration with IIT-Delhi, IIT-It also assessed the capability of IZO films to replace conventional FTO-based glasses as transparent conductive oxides. IIT-Delhi samples were optically and electrically characterized and tested in DSSC devices. Unfortunately, the huge resistivity of the IZO films delivered reduced performances compared to standard FTO-based devices.
WP3 - Operational mechanism/Electrolytes. The work is organized into three tasks, involving modelling of dye-sensitized heterointerfaces, synthesis of new electrolytes, spectroscopic investigations and fabrication and testing of DSC devices.
D3.1 - This deliverable deals with the successful accomplishment of the model set up aimed at understanding the interdependencies of the various standalone materials employed in DSCs. A main understanding needs to be achieved concerning the dye adsorption onto the TiO2 surface, which in some respect represents a main dye characteristics along with the dye/semiconductor/electrolyte alignment of energy levels. This information, integrated by that obtained from D3.2 will allows us to gain unprecedented knowledge of the factors affecting the DSCs photovoltaic performances, thus allowing us to cast new criteria for the design of novel materials with unprecedented performances. The three main DSCs constituting materials, i.e. the dye, the semiconductor oxide and the redox shuttle, have been investigated in a coherent fashion by employing state of the art first principle computational techniques and developing novel approaches for the description of dye sensitized semiconductor interfaces. The work was organized along the following three main lines:
1) Dye adsorption onto TiO2 surfaces, Figure 6.
In an effort to design new and more stable and efficient dyes, it is fundamental to disclose the anchoring mode of the most commonly employed sensitizers on the semiconductor surface. The dye anchoring group indeed promotes electronic coupling between the donor levels of the excited dye and the delocalized acceptor levels of the semiconductor, assisting the charge injection process. Also, the orientation and packing of adsorbed dyes on the semiconductor surface strictly depends on the binding configuration, affecting the rate and effectiveness of parasitic recombination reactions. Finally, the dye anchoring group provides the required stable dye grafting onto semiconductor surface, thus leading to long-term device stability.
2) Influence of the Dye Molecular Structure on the TiO2 Conduction Band, Figure 7.
Finally, considering the intimate dye/semiconductor interaction, assessing the origin of the shifts induced by surface adsorbed dyes or co-adsorbents on the energy of the TiO2 conduction band is of paramount importance.
3) Modeling dye/semiconductor/electrolyte interactions and alignment of energy levels.
A further important dye characteristic is the matching of ground and excited state oxidation potentials with the redox shuttle and semiconductor conduction band, respectively. These energetic requirements rule the DSCs kinetics and are effectively needed to allow for efficient electron injection into the semiconductor manifold of unoccupied states and subsequent regeneration of the oxidized dye.
The iodide/triiodide (I-/I3-) redox couple has maintained a clear lead in DSCs for many years, although this system is now being rivaled by the Co(II)/Co(III) redox couples, with the record DSCs efficiency obtained by a Co(II)/Co(III) liquid electrolyte.2
D3.2 – We focused on the understanding of fine interfacial TiO2/dye phenomena. As a matter of fact, the modelling of the devices operational mechanisms requires the accurate description of both isolated cell components and dye/electrolyte/semiconductor interface. The dye, the semiconductor oxide and their interface have been investigated by employing state of the art experimental and first principle computational techniques. The work was organized along the following three main lines
1) Structural, electronic and optical properties of new semiconductors nanostructures
We investigated the effect of structure and solvent dynamic on the optoelectronic properties of realistic ZnS quatum dots (QDs), showing that inclusion of explicit water molecules in in the simulation plays an important role on the structure of the investigated QDs by lowering the surface energy and stabilizing a bulk-like geometry. We also found that the dynamic behavior of the ZnS QDs is reflected in their optoelectronic properties: the band-edge states vary continuously along the trajectory of the molecular dynamic simulation. We also carried out an accurate computational analysis on the nature and distribution of electronic trap states in shape-tailored anatase TiO2 structures, investigating the effect of the morphology on the electronic structure. Linear nanocrystal models up to 6 nm in length with various morphologies have been investigated by DFT calculations. Our results point at the crucial role of the nanocrystal morphology on the trap state density, highlighting the importance of a balance between the low-energy (101) and high-energy (100)/(001) surface facets in individual TiO2nanocrystals.
2) Spin-orbit coupling effects in Ruthenium and Osmium Dye-Sensitized Solar Cells
We have performed relativistic TDDFT calculations employing a novel computational approach to evaluate the impact of spin−orbit coupling (SOC) in the optical and photovoltaic properties of panchromatic Ru(II) and Os(II) dyes.The employed computational setup accurately reproduces the optical properties of the investigated dyes, allowing an assessment of the factors responsible for the varying SOC with the dye metal−ligand environment.
3) Modelling the dye/semiconductor interface
Employing joint theoretical and computational approaches we have addressed different issues in the structural, electronic and optical properties of various TiO2/organic-dye and TiO2/perovskites interfaces. We modelled: 1) the anchoring of a di-branched organic dye; 2) the optical response changes in going from solvated to TiO2-anchored dye; 3) the effect of the substrate protonation in the optical and charge transfer properties of the dye/TiO2 interface; 4) the effect of the molecular dynamic in the rate of hole diffusion in a dye monolayer; 5) the generation of Sark effects at the perovskite/TiO2 interface. In all the presented cases, the employed high-level computational methodology has been proved to nicely reproduce the experimental data and provide important insights into the interpretation of the interfacial phenomena and device functioning mechanism.
D3.3 - CNR and EPFL reported the screening of the novel electrolytes synthesized in India, along with providing the basic understanding of the DSCs operational mechanism with the new electrolytes. To meet this objective, the joint EU-India team (EPFL, CNR and IICT) designed, synthesized, characterized and tested in DSC devices a new class of cobalt electrolytes, along with a new variant of the previously reported tri-bipyridine cobalt salts. The investigated electrolytes are listed below:
1. [Co(Cl-phen-terpyridine)2]2+/3+ [TFSI]2/3
2. [Co(bpy)3]2+/3+ [TFSI]2/3 and [PF6 ]2/3
The [Co(Cl-phen-terpyridine)2]2+/3+, synthesized by IICT-India, is the first of a novel class of substituted phenyl-terpyridine cobalt complexes, which have never been employed as electrolytes in DSCs. The [Co(bpy)3]2+/3+ is on the other hand the standard cobalt DSCs electrolyte. For this system we investigated the effect of the electrolyte composition, in terms of additives, and of different counterions (e.g. TFSI vs. PF6). A sample of the [Co(bpy)3]2+/3+[PF6 ]2/3 complexes was also provided by IICT. The synthetic and photovoltaic studies are complemented by FT-IR and computational modeling investigations.
While the novel phen-terpyridine-based electrolyte exhibits lower performances compared to the standard bpy-based one, and for the same bpy-based system we show the TFSI salt to be slightly inferior to the PF6 salt, we show that in all cases by simply adding an inexpensive additive to the standard cobalt electrolyte, high photovoltaic efficiency can be obtained with standard dyes, further expanding the scope of iodine-free electrolytes.
The three fundamental problems in the atomistic modeling of dye-sensitized semiconductor interfaces, mentioned above on deliverable D3.1 were individually investigated to reach a deep insight into the corresponding problems, allowing us to gather at the same time a global knowledge of their interdependencies in determining the DSCs photovoltaic performances. As such, this deliverable represents the successful accomplishment of this milestone.
D3.4 -. In this deliverable we reported the investigation on a new counter-electrode catalyst, Cobalt Sulphide, for Dye-sensitized Solar Cells (DSCs) employing a tris-bipyridine cobalt-based electrolyte. This research was carried out in collaboration between the EPFL and IIT Delhi.
Cobalt Sulphide films were deposited on the conductive glass substrate through a potentiodynamic method, in various experimental conditions. The obtained counter-electrodes have been characterized by many experimental techniques and they have been used for the fabrication of DSCs employing the C218 organic sensitizer and the [Co(bpy)3(TFSI)]2/3 redox electrolyte. Comparison between the new counter-electrodes and the traditionally used Pt ones have been performed, obtaining comparable efficiencies close to 7%. Cobalt Sulphide can thus be considered as a promising alternative to Pt for the application as counter-electrode catalyst in DSCs in combination with cobalt based redox electrolytes
WP 4 - Lifetime/Modules. The work is organized into three tasks, dealing with device optimization for selected materials developed in WP1-3, fabrication of 10cm2 modules and testing of device stability under heat and light soaking conditions.
D4.1 - The subject of D4.1 is to “Perform accelerated testing at 85 °C/85% relative humidity (RH) on state of the art cells” (standard test IEC 61646). In order to meet these requirements, it was decided to undertake some preliminary tests, light soaking (1 sun, ~55 °C), thermal stress test (85 °C / 5% RH), and at the end damp heat test (85 °C / 85 % RH). Initial results from light soaking indicated promising stability with only 5% relative loss of performance after ~3400 h. Unfortunately, initial results from thermal stress at 85 °C were less encouraging with efficiencies showing ~60% relative loss of performance after less than 300 h. The degradation mechanism is still not well understood at this point. Several actions are in progress in order to improve the cell stability at high temperature (>80 °C). Our preliminary damp heat testing showed mixed results. A combination of materials enabled us to obtain good results at temperatures up to 75 °C without major degradation and loss of performance. However, the same test performed at 85 °C permanently damage the cells due to sealing failure and other degradation mechanisms seen on the thermal stress long term testing. New encapsulation methods were used and enabled us to prevent cells from delaminating, and performance loss after testing was reduced (~15-20% loss). At high temperature (>70 °C), it is important to use Bynel® instead of Surlyn®, as Bynel® has a higher melting point, as well as to employ a higher boiling point solvent containing electrolyte (HBS). Experiments are now in progress to assess several combinations of sealing materials and encapsulation methods to overcome the delamination problem and further reduce performance loss at high temperature humidity. Once the degradation issues at the macro scale are overcome, it will enable us to fabricate robust DSC cells and focus on understanding the failure mechanisms at the molecular level.
As an additional work, a strong collaboration has been set-up within the EU-India joint consortia involving DSL and CNR from the EU side and IICT from the India side, to investigate the durability assessment of IICT’s Y1 dye, which is of commercial interest to Dyesol, and to simultaneously carry out modelling to understand the experimental results and facilitate future predictions of material and device characteristics. Y1 and Y2 dyes from IICT have been shipped to DSL and CNR has calculated the binding energies of these dyes against the Black Dye on TiO2. This topic will be the subject of an EU-India joint publication.
D4.2 - In this deliverable Dyesol aims to “improve temporal stability of 1cm2 cells by 15% over state of the art” according to standard test IEC 61646. We also report stability assessment of DSCs based on new Ru(II) dyes and on cocktail dyes synthesized by IICT-India.
To meet the stability requirements, we focused our work on the two main tests, i.e. light soaking (1 sun, ~55°C) and damp heat test (85°C/85% RH), and several materials (dyes, electrolytes, seals…) were tested. All the results are obtained for standard 8.8x11 mm2 cells (0.88 cm2), which are the standard Dyesol test cells. These are small elements extracted directly from the geometries of larger tiles, so the results can be safely scaled to larger dimensions.
Results from light soaking indicated good stability up to ~8000h, with only 8% relative loss of performance. A 19% performance drop after ~11000h was however also observed. We were able to get good results also at the damp heat test, with only a 5% loss of efficiency (at 1 sun) after ~1900h, using cells prepared with 18NR-AO TiO2 paste,TiCl4 OL, Z907 dye, Bynel® 80 μm and HBS-based electrolyte. An epoxy secondary sealing was also applied. Cells were further sealed in a metal-polymer pouch. Encouraging results were obtained for heat test (85°C, dry atmosphere) with an efficiency loss of only 3.2% after 1000h (at ⅓ sun) with the Z907 dye, Surlyn® 50 μm, HBS-2-BI electrolyte and epoxy secondary seal.
Our new device fabrication setup enables us to prepare robust cells that meet the requirements for the standard test IEC 61646. We have seen the positive effect of under and over-layer on cell performances and stability of the seals; we have optimised the epoxy secondary seal and started to investigate the use of a very promising metal/polymer pouch as tertiary seal.
Stability assessment of the dyes synthesized in India was performed by considering N749-Y1 (from IICT-Hyderabad) cocktails. These DSSCs show much higher efficiencies compared to N749 or Y1 alone (~+16%) and also show also a good stability after ~2000h of long-term light soaking test, with no loss of performance.
Additional stability data (albeit on smaller cells) were gathered for the new MC112 ruthenium dye, synthesized by IICT-India and reported in WP1, for which we got essentially no efficiency decrease after 1000h of long-term light soaking.
D4.3. We have successfully fulfilled both milestones (MS10) and (MS11), which are respectively “fabricate 10+ cm2 modules with less than 35% drop in efficiency as compared to 1 cm2 cell performance” and “fabricate 10 cm2 modules and demonstrate 10,000 hr stability with less than 20% degradation in efficiency”.
Best modules (~42 cm2) have a starting efficiency of 7.1% with a ~15% loss of performance (~6%) after more than 12200 h (which is more than 16 months continuous illumination), Figure 8.

WP 5 - Management. Management activities were organized to set up and run the project decision-making bodies, to take care of the dissemination of the project achievements and training, and to exploit the IP produced by the project.
Very intensive management activities were needed for reporting, to coordinate the EU-India consortia and to organize the DSC Summer School.
The specific objectives of WP5 are:
-Lead the ESCORT project to technical, organisational and financial achievement;
-Set up and run the project decision-making bodies;
-Organize training activities;
-Ensure the exploitation of commercially interesting developments achieved by the project;
-Recognise developments within the project for which intellectual property should be protected;
-Provide Reports and other Grant Agreement requirement.
-Run the ESCORT web site.
-Ensure proper dissemination of the project outcome.
D5.2 - The periodic report due at month 30 was duly submitted, which allowed the coordinator to check the status of the EU and joint EU-India activities.
D5.3 - We have organized the ESCORT Summer School on Dye-sensitized Solar Cells. This took place at the Indian Institute of Chemical Technology (IICT) in Hyderabad, India, on August 8th , 9th and 10th 2013, together with the Celebration of the 70th anniversary of IICT foundation, Figure 9.
The summer school was based on lectures delivered by at least one representative of the ESCORT project partners, plus additional external invited speakers from India and from other asian countries. Some of the non-indian speakers have been invited on the EU-ESCORT budget, while all the indian speakers have been invited on the DST-ESCORT budget. The accomodation expenses for all the invited speakers have been covered by the DST-ESCORT budget.
The summer school/symposium was a big success, with about 100 participants, out of which 60 graduate and undergraduate students. A prize for the best poster has been awarded to the best 3 poster presentations. During the Summer School we also organized the annual ESCORT General Meeting.
We organized an informal intermediate meeting in December 2011 at the EPFL premises in Lausanne. All the partners have interacted at least weekly by skype calls and email.
D5.4 - The periodic report due at month 48 was duly submitted, which allowed the coordinator to check the status of the EU and joint EU-India activities meeting the requirements of the corresponding milestone (MS12).
WP 6 - Scientific coordination. This WP is intended to organize the project meetings and to coordinate the Exchange Mobility Program.
D6.1 - Organization of the ESCORT’ General Meeting.
The first ESCORT General Meeting, after the kick-off meeting, was held at the CNR headquarters in Rome , Piazzale Aldo Moro 7 - Italy, on July 26th 2012. 19 delegates from India and Europe attended the General meeting, see the list of participants in Table 2. At least one delegate from each project partner was present at the meeting. The second ESCORT General Meeting has taken place at the Indian Institute of Chemical Technology (IICT)in Hyderabad, India, on August 9th 2013. Each partner attended the meeting with at least one representative, Table 3. The ESCORT Final Meeting took place at the École Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland, on May 11th 2014. 10 delegates from India and Europe attended the General meeting, see the list of participants in Table 4.
So far we organized an informal intermediate meeting in December 2011 at the EPFL premises in Lausanne. All the partners interact at least weekly by skype calls and email.
D6.2 - ESCORT Exchange Mobility Program.
The exchange mobility programme has organized 20 visits of 11 researchers from/to India and Europe, see Table 5 for a summary of the exchange visits.

Potential Impact:
All the objectives of the ESCORT project were well beyond the state of the art, in terms of synthetic/production strategies, of basic knowledge being developed and of their integration into new and more efficient devices. To a large extent, the project has been unexpectedly successful in this ambitious aspiration.
The integrated approach that we have developed and applied clearly demonstrated the development of more stable and performing individual DSCs components, along with their integration into new and more efficient devices. This latter aspect represents a strong added value of our project, which was effectively realized only by means of the cooperation between the leading groups in DSCs technology that we collected. Moreover, this project has represented an opportunity for the European industry to exploit such a consolidated leadership in nanotechnology and materials science based in Europe, and translate it into highly efficient photovoltaic solar energy devices based on cheap materials and processes, with high potential for the Indian markets. The joint EU/India activities were strategic in consideration that the Indian economy is growing and needs more and more energy to maintain its growth (at least growth of that part of India, which is growing). There are around 640,000 villages in India, accounting for about 70% of the population. Of these, according to GOI, in 2004, 475,000 (i.e. around 74%) villages were "electrified". Since independence, India had made strides in Rural Electrification, increasing the number of electrified villages from 1,500 in 1947 to 481,124 villages by 1991. After that, however, as a part of the "liberalisation" and "reforms" process, a number of villages were "de-electrified", decreases the number to 474,928 by 2004. Presently, the Indian population in unelectrified villages invariably use fire-wood for cooking purposes which is obtained by deforestation resulting global warming. For lighting purposed, kerosene lamps are being used which is obtained from depleting fossil fuel reserves. India is mainly depending on thermal and hydro electric power. But, the resources will not be sufficient to meet our requirement. However, recently, Government of India took initiatives to introduce and subsidies, LEDs devices which can be operated at low voltages. Alternative energy sources like wind and nuclear power are also limited in India. Solar power, on the contrary, is the only technology which is capable of doing so far into the future, provided a sufficiently cheap and efficient technology emerges. Within the solar photovoltaic framework, the market is presently dominated by so-called “1st generation” PV. 1st-gen PV, a.k.a. silicon PV (in either single-crystalline or poly-crystalline form), is an old technology dating from the 1950’s, and has had a long development cycle to reach its present status. Notwithstanding his rapid growth, PV energy generation still only accounts for a measly single digit percentage of global energy production. While more “newcomers” are entering the commercialised technology space in the form of 2nd-generation PV (CdTe, CIGS, amorphous silicon, etc.), these technologies have not yet reached superior commercial prospects except in narrowly defined roles such as low-cost CdTe cells for remote solar farm applications. What is missing from the equation to date is a true low cost, widely deployable, easily manufactured and rapidly scalable technology. Incumbent PV technologies of the 1st and 2nd generations simply cannot meet these requirements for a variety of reasons, such as energy intensive manufacture, or resource limitations of raw materials, for instance. The work within ESCORT has made a significant advance of 3rd generation PV technologies and will in the future lead to an extraordinary advance in well-being and societal wealth, only previously witnessed with the discovery of oil. 3rd generation PV technologies are truly globally scalable, with no resource limitations, highly scalable and cheap manufacturing routes for both materials and panels, and extremely flexible deployment options valid for both traditional markets (solar farms, rooftop panels, etc.), as well as more fundamentally market-changing applications such as building integrated photovoltaics (BIPV). Although there is still a long road towards such globally significant deployment, the initial foundational framework for the inevitable success of this novel technology has been securely laid within the ESCORT project and its impressive technological gains. Our technical objectives have been chosen to impact in the future thin film PV industry, that is manufacturing, supply of manufacturing tools, supply of raw materials, cost competitiveness of PV, sustainability of the PV market, stability of the solar cells. Downstream impacts are expected in growth of the PV market, PV systems, de-carbonization and climate stabilization and in the critical need for sustainable energy in emerging economies. Moreover, from the Indian point of view, we aimed to provide technology for the “common man” in India for utilization of solar photovoltaics. Even small DSC devices can support LED lighting devices particularly important in small Indian villages to avoid utilization of kerosene lamps and the consequent deforestation process. Also, the new DSC technology can be used to operate refrigerators, necessary to store vaccines and life saving drugs, and thus improving the health of rural indian population, as the medical facilities are concentrated only in urban areas. So, the developed DSC technology can improve the life standards (literacy as well as health care) particularly in Indian villages and can contribute to the reduction of global warming. Particular societal impact is also expected from the climate and environmental benefits due to the replacement of conventional energy sources by low-energy/low-cost yet efficient and stable photovoltaic solutions.
Exploitation of the ESCORT results has been monitored by Dyesol. Dyesol maintains a core business element of raw material supply for 3rd generation photovoltaics. Dyesol continues the commercialisation of dye-sensitised solar cells and related ESCORT technologies, and has successfully advanced the production feasibility of ESCORT DSCs technology on various substrates including metal foil. Production of perovskite based ESCORT technology is an expanding area of commercial interest for Dyesol. Beyond this, Dyesol has revised its business plan to accommodate the commercial opportunities represented by the changing playing field in 3rd generation photovoltaics, a not insignificant contributing element to which was the outputs of the ESCORT project.
As clear examples of the achieved outstanding scientific and technological results, we remark that the developed dye-sensitizers represent absolutely the cutting edge of the research in the field, as demonstrated by the new DSCs world record of 13.5% set by our single-porphyrin dye reported in D1.2. Similarly, the nanostructured electrodes developed in D2.1 have achieved among the highest performance ever reported for non-nanoparticulate TiO2. And, more importantly, the optimization of the DSSCs based on inorganic perovskite absorbers processing with an organic hole conductor, carried out in collaboration with IIT-India and reported in D2.2 led to a photovoltaic efficiency of 12.6%, one of the highest values obtained with perovskites inorganic absorbers. Also, the anti-reflective/self cleaning coatings with enhanced properties reported in D2.3 will have impact in the entire field of photovoltaics, beyond the DSCs field. The interplay between academic research and industrial partners has clearly led to the coherent development of the DSCs technology, which will enable its rapid subsequent industrialization. This is demonstrated by D4.2 in which we have reported that 1 cm2 DSCs have passed the standard test IEC 61646, promising comparable stability to that of conventional photovoltaics.
Up-scaling of the developed DSCs technology was also a key target of the present project. The DSCs technology developed within ESCORT is competitive with incumbent 1st and 2nd generation PV systems, for such applications as solar farms or more traditional rooftop mounted arrays. A major breakthrough of the ESCORT project was the achievement of two milestones MS10 and MS11 i.e. “fabricate 10+ cm2 modules with less than 35% drop in efficiency as compared to 1 cm2 cell performance” and “fabricate 10 cm2 modules and demonstrate 10,000 hr stability with less than 20% degradation in efficiency” have been successfully achieved.
These results, together with the ensemble work performed by the industrial partners, has allowed the project to pass the standard test IEC 61646, promising comparable stability to that of conventional photovoltaics.
A strong contribution to the results achieved so far has come for the interplay between the EU and India consortia, which has led to several materials and researchers exchange. Mobility exchange programs has been mainly oriented towards training Indian partners on specific subjects of common interest for the project, e.g. members of the CNR partner have trained some members of the IICT partner towards the use of DFT calculations in predicting the dye properties, thus achieving a maximum throughput of their dye production in the context of the ESCORT project. Members of the EFPL and IIT-It partners have trained Indian partners (IIT-In) towards photovoltaic characterization and DSC fabrication techniques and nanostructured oxide preparation methods, respectively. We have activated the Exchange Mobility Program, with the visit of Dr. Giribabu to EPFL in December 2011 and visits of IICT-India researchers to EPFL and CNR in May 2012. In occasion of the ESCORT annual meeting, in July 2012, we organized a visiting period for IICT and IIT-India researchers to stay in EPFL, CNR and IIT. In December 2012, a student from CNR visited IICT. Dr. Bhanuprakash Kotamarthi (IICT-Hyderabad) visited CNR laboratories in November 2013. From 1st October to 18th December 2013, a student from IIT-Delhi visited EPFL laboratories. In 2014 we organized a visiting period for IICT researchers to stay in EPFL, IIT and DSL.
Also, as part of the required activities by our joint Grant, we have organized the ESCORT Summer School on Dye-sensitized Solar Cells. This took place at the Indian Institute of Chemical Technology (IICT) in Hyderabad, India, on August 8th , 9th and 10th 2013, together with the Celebration of the 70th anniversary of IICT foundation. The DSC summer school was based on lectures delivered by at least one representative of the ESCORT project partners, plus additional external invited speakers from India and from other asian countries. Some of the non-indian speakers have been invited on the EU-ESCORT budget, while all the indian speakers have been invited on the DST-ESCORT budget. The summer school/symposium was a big success, with about 100 participants, out of which 60 graduate and undergraduate students. A prize for the best poster has been awarded to the best 3 poster presentations. The organization of the DSCs summer school in Hyderabad has been an excellent occasion of outreach to demonstrate the potential of the DSCs technology. An obvious consequence of the project outcome is the expected societal climate and environmental benefits due to the replacement of conventional energy sources by low-energy/low-cost yet efficient and stable photovoltaic solutions.
In order to highlight the project achievements, the partners of the ESCORT consortium have participated to several international conferences on DSC, like the European Materials Research Society (E-MRS) conferences, the Hybrid and Organic Photovoltaics Conferences and the International Conferences on Simulation of Organic Electronics and Photovoltaics (SimOEP).
In addition, CNR has organized three “hands on” dissemination events (in June 2011, May 2012 and March 2013) for school kids in the city of Perugia, Italy, in which CNR researchers involved in the ESCORT project have illustrated the DSC technology and taught kids how to make solar cells based on fruit juices.
CNR has also participated to the “Researchers Night” event in Trieste, Italy, where it was invited and hosted by the International School of Advanced Studies (SISSA).
The project web-site is considered the major dissemination medium of the project outcome. Thus, the ESCORT web site was set up and is constantly updated, (see http://www.escort-project.eu).

Concerning exploitation of IP produced by the project, Dyesol has a key responsibility under WP5 both in EU and India, in relation to the industrial partners participation to the project. Work was undertaken on initial evaluation of the existing IP situation in respect to materials, devices, designs, etc., pertinent to the ESCORT project. This work assisted the Coordinator in drafting the Consortium and Coordination agreement, to ensure a proper exploitation of the IP generated by the project.
The EU and India work plans were managed to have strong connections. It was also ensured that the possibly different timings of projects evolution from the EU and Indian side led to no “waiting for input” idle time on each side.
Dyesol have constantly monitored the published literature in the DSC field.

All scientific advances achieved by the ESCORT project has been published in peer-reviewed journals. We published a total of 70 publications in international peer-reviewed journals, of which 12 EU-India joint publications. All publications have been provided open access (with the exception of three papers for which no agreement was concluded with the publisher), thus strongly increasing the dissemination of the project outcome to the wide public.
All consortium members have partaken in public outreach activities at their respective institutions, which are ideal platforms to inform the public of current pressing scientific issues. The team at EPFL have developed an exceptionally well received schools out-reach project, where each year hundreds of school children in Geneva partake in a session making dye-sensitized solar cells using basic commodity materials and blackcurrant juice as the dye. Within the consortium this specific outreach project will be branded, and all members has incorporated it into their current university outreach activities, significantly increasing the exposure of school children to this future technology across Europe. Along with this targeted activity, the CNR member of the ESCORT project have contributed to the organization of the HOPV conference series (www.hopv.org) with scheduled meetings in 2011, 2012, 2013 and 2014. To ensure exploitation of the advances, the ESCORT project is based on the appropriate participation of the research and industrial partners. Three industrial partners from EU/India, two of them already active in the photovoltaics field for many years and one (DSL) leading the industrial development of DSC, guarantees efficient dissemination of the results, effective technology transfer and direct uninhibited exploitation of the new knowledge from Europe and India. In this way Europe will retain and strengthen its position at the forefront of the emerging technology of DSC while exploring and creating new market opportunities in India and for India in the EU. All commercial exploitation possibilities will be considered, to maximize the commercial impact of the project, including licensing to the commercial partners, licensing to non-partner commercial entities, and setting up new commercial ventures in the form of spin-out companies. At any appropriate stage of the implementation, the consortium will endeavor to make best use of the exploitable results of the project, in particular those with a commercial potential, through its own resources, CORDIS or other external services. This may include proof of concept outside the laboratory; the identification of market potential and opportunities; the evaluation of competing technologies; the assessment of the cost for upscaling from lab scale to industrial application; the development of a business plan; protection of intellectual property rights; etc.

List of Websites:
The ESCORT web site, constantly updated, can be reached at www.escort-project.eu

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