Novel conjugated polymer structures for high efficiency all-organic solar cells

1. Novel conjugated polymer structures for high efficiency all-organic solar cells PN-II-ID-PCE-2011-3-0274/Contract nr. 148/2011 Project manager: Dr. Ing. MirceaGrigoras PetruPoni Institute of Macromolecular Chemistry - Iasi, Institute of Excellence of the Romanian Academy Tel.: +40-0232-260332/117 E-mail: grim@icmpp.ro

2. Summary • Research team • Objectives • Project value • Project stage:-Phase 2012 • -Phase 2013 • Results dissemination • Articles • Participation on different symposia

3. Summary Photovoltaic devices are considered one of the important scientific and technological challenges for conversion of the most important source of inexpensive and renewable energy (solar energy) to electricity. However, traditional photovoltaic silicon solar celles are still deemed too expensive to be a serious concurrent to fossil fuels or other renewable energy sources (wind, waterpower, biomass, etc.). All-organic solar cells are considered now as being a very promising alternative for conversion of solar energy to electricity because they can be fabricated based on low-cost advanced materials and using the bulk heterojunction technology. Energy diagram of an organic solar cell based on BHJ concept; The four subsequent processes to generate photocurrent are: (1) absorption of an incident photon to create an exciton, (2) diffusion of an exciton toward the donor-acceptor interface, (3) dissociation of an exciton into an electron in the acceptor and hole in the donor, and (4) collection of charges at the contacts.

4. Research team • Project manager • Dr. MirceaGrigoras • Dr. AncaStanculescu • Dr. LoredanaVacareanu • Dr. Marcela Socol • Dr. Ana-Maria Catargiu • Dr. Teofilia Ivan • Drd. Oana-IulianaNegru • Asit. OlticaTescu

5. Objectives • The general objectiveof this proposal is to bring an original contribution to understanding in more detail of the photovoltaic process in organic materials by synthesis of novel conjugated donor polymers with efficient sunlight absorption on a large spectral domain and good hole transporting materials by modification and manipulation of the chemical structures of the conjugated polymers and architecture. • Synthesis and characterization of new donor conjugated polymers • Synthesis and study of oligomers with branched, star and dendrimer structure • Functionalization of acceptors • Synthesis of photoactive layers by molecularly dispersion of acceptors in polymers

6. Project value Stage 2012: 550000 lei Stage 2013: 225745,43 lei Stage 2014: 724254,57 lei Total Budget: 1500000 lei

7. Project stage: Phase 2012 • Objectives: • Synthesis of new monomers based on carbazole as 2,7- disubtituted ring and to use in synthesis of polyarylenes and polyarylenevinylenes • The synthesis of polymers in different conditions, their characterization and optoelectronic properties (UV-Vis,fluorescence spectra and electrochemical behavior [HOMO, LUMO levels, Eg]) • Synthesis of oligomers and dendrimers based on triphenylamine and benzene by Suzuki, Wittig or Heck reaction and their chemical characterization.

8. Results dissemination 2012 • Articles • 1. Synthesis of Poly(arylene vinylene)s Containing Carbazole, Triphenylamine and Phenothiazine Rings in the Backbone by a Cascade Suzuki-Heck Reactions, T. Ivan, L. Văcăreanu, M. Grigoras, International Journal of Polymeric Materials, published early view, DOI: 10.1080/00914037.2012.664206,(2012).Publish: 62(5), 27-276 (2013), FI (2012) =1.865. • 2. Synthesis of star poly(N-vinylcarbazole) by microware assisted reversible addition-fragmentation chain transfer polymerization (RAFT); M.Grigoras, O. I. Negru, Polymers, 4, (2), 1183-1194, (2012).Doi: 10.3390/polym4021183; www.mdpi.com/journal/polymers, FI (2012) =1.687. • Synthesis and optoelectronic characterization of some star-shaoedoligomers with benzene and triphenylamine cores , T. Ivan, L.Vacareanu, M.Grigoras, ISRN Organic Chemistry, , DOI:10.5402/2012/976178 (2012), article ID 976178, 11 pages, FI (2012) = 1. • Photophysical properties of isoelectronic oligomers with vinylene, imine, azine and ethynylene structure containing triphenylamine and carbazole moieties, M. Grigoras, L. Vacareanu, T. Ivan, A.M. Catargiu, Dyes and Pigments, sumitted for publication (2012) early view: http:/dx.doi.org/10.1016/j.dyepig.2013.01.025, Publish: 98, 71-81 (2013) FI (2012)= 3.532.

9. 5. Synthesis and photophysical properties of two intramolecularchharge-tranferchromophores obtained by [2+2] cycloaddition of TCNE and TCNQ to an electron rich alkyne, T. Ivan, L.Vacareanu, M.Grigoras, Revue de Chimie, (sumitted for publication 2012). :64(4), 372-377, (2013), FI (2012) = 0.538. • 6. Linear and Hyperbranchedtriphnylamine-based polyarylenevinylenes: A comparative optoelectronic study, T. Ivan, L.Vacareanu, M.Grigoras, Design Monomers and Polymers, (2012)early view:http://dx.doi.org/10.1080/15685551.2013.840495, FI (2012) =0.875. • Synthesis and photophysical properties of the two branched carbazole-based polymers; A. M. Catargiu, T. Ivan, L.Vacareanu, M.Grigoras, Revue Romanine de Chimie, Dedicated to Professor Bogdan C. Simionescu on the ocassion of his 65th birthday, (sumitted for publication 2012), FI (2012) =0.331. • Polyaniline/Poly (aniline-N-propansulfonic acid) composites by template polymerization of aniline; A. M. Catargiu, M.Grigoras, Proceedings of Conference: Advanced Topics in Optoelectronics, Microelectronics and Nanotechnologies8411, 84111G1-G10, doi:10.1117/12.974919, (2012).

10. PhD Thesis 1. Synthesis of new oligomers and polymers fluorescent arylamine-drd. Teofilia Ivan, conducator stiintific Dr. Mircea Grigoras-sustained in November 2012).

11. Communications 2012 • The 6th Edition of the International Conference: Advanced Topics in Optoelectronics, Microelectronics and Nanotechnologies, Constanta, 23-26 August 2012 • Polyaniline/Poly (aniline-N-propansulfonic acid) composites by template polymerization of aniline; A. M. Catargiu, M.Grigoras • A XXXII-A Conferinta Nationala de Chimie, Calimanesti-Caciulata, 3-5 Octombrie 2012 • Synthesis and opto-electrochemical properties of two 2,7-carbazole-based conjugated polymers; A. M. Catargiu, M. Grigoras, • Synthesis and characterization of poly(ethyl methacrylate) via atom transfer radical polymerization using a triphenylamine derivate as initiator; O. I. Negru, M. Grigoras • The XVII-th International Conference: Psysical Metods in Coordinationand Supramolecular Chemistry, Chisinau, Republica Moldova, 24-26 Octombrie 2012 • Formation of inclusion complexes between cucurbit[6]uril and aniline monomers; A. M. Catargiu, M. Grigoras,

12. Posters 2012 • 7th International Conference Nanostructured polymers and Nanocomposites, Prague, Czech Republic, April 24 – 27, 2012 • New branched arylamine-based poly(arylenevinylene)s with possible applications in optoelectronic devices, T. Ivan, L. Văcăreanu, M. Grigoraş, • Optical complexation studies and electrochemical characterization of two aromatic oligoimine, L Vacareanu, T. Ivan, M. Grigoras • International Workshop on the Electrochemistry of Electroactive Materials- Szeged- Hódmezővásárhely, Hungary, June 3 - 8, 2012 • Electrochemical characterization of a triphenylamine-based atom transfer radical polymerization initiator and its polystyrene macromonomer, O. I. Negru, M. Grigoras • 4th Bilateral symposium on Functional heterocyclic and heterochain polymers for advanced materials, Iaşi, 2 - 7 septembrie, 2012 • Tuning of optoelectronic properties of poly(4,4’-triphenylamine-vinylene)s by post-modification reactions, T. Ivan, A. M Catargiu, L. Văcăreanu, M. Grigoraş

13. Project stage: Phase 2013 • Objectives: • Synthesis and characterization of new conjugated oligomers and polymers with donor groups. • Synthesis of photoactive films of conjugated oligomers and polymers with donor groups and small molecular acceptors. • Dissemination of scientific results.

14. Dissemination of results- 2013 • Articles Grafted Polytriphenylamines Synthesized by Tandem Atom Transfer Radical Polymerization and Oxidative Polycondensation, O.I. Negru, M. Grigoras, Iranian Polymer Journal, submitted for publications (2013), early view: DOI 101007/s13726-013-0163-1, Published : 22(9), 641-651 (2013), FI (2012) = 1.053. Polytripenylamine synthesized by interfacial and microemulsion oxidative polymerization, Colloid and Polymer Science, O.I. Negru, M. Grigoras Received: 12 ianuarie (2013), accepted 13 august (2013), early view: 10.1007/s00396-013-3055-1, FI (2012) = 2.161. Synthesis and optoelectronic characterization of some triphenylamine-based oligomers containing strong acceptor substituents, Mircea Grigoras, Teofilia Ivan, Loredana Vacareanu, Ana Maria Catargiu, Journal of Luminescence, Manuscript LUMIN-S13-01096 , FI (2012) = 2.144. Tuning optoelectronic properties of poly(4,4’-triphenylamine-vinylene)s by post-modification reactions, Ana Maria Catargiu, Teofilia Ivan, Loredana Vacareanu, Mircea Grigoras, Synthetic Metals, sumitted in September 2013. FI (2012) = 2.109. A comparative study of optical and electronic properties of arylenevinylene and aryleneethynylene polymers containing 2,7 and 3,6 disubstituted carbazole units, A. M. Catargiu, M Grigoras, Journal of Optoelectronics and Advanced Materials, sumitted for publication July 2013, FI (2012) = 0.46.

15. PhD Thesis Studies on the synthesis of polymers with chromophore grousp by controlled radical polymerization-drd. Oana Iuliana Irimia (Negru), conducator stiintific Dr. Mircea Grigoras-sustained in October 2013).

16. Communications 2013 • Zilele Universitatii "Alexandru Ioan Cuza" din Iasi, Conferinta Facultatii de Chimie&Mini Hot Conference: Recent Achievements in Organic and Supramolecular Chemistry, 31 Octombrie – 2 Noiembrie 2013, Iasi • Synthesis, spectral stability and photoluminescent properties of arylenevinylene polymers containing 2,7 - carbazolyldiyl and 3,6 – carbazolyldiyl moieties in the main chain ;Ana-Maria Catargiu, Loredana Vacareanu and Mircea Grigoras. • Synthesis and characterization of poly(triphenylamine)-g-poly(ethyl methacrylate) using in tandem controlled radical polymerization and chemical oxidative polymerization;O. I. Negru, M. Grigoras. • 14th edition of the annual TIM International Physics Conference, TIM 2013-Hosted by the West University of Timisoara, 21st – 24th of November, Timisoara, Romania • Spectroelectrochemistry approach as a tool for in-situ optoelectronic and electrochromic properties investigation of some polymers containing carbazoleunits:Loredana Vacareanu , Ana-Maria Catargiu and Mircea Grigoras.,

17. Posters 2013 • 11th Conference on Colloid and Surface Chemistry", Iasi, 9 - 11 Mai, 2013 • The synthesis of grafted polytriphenylamine using in tandem atom transfer radical polymerization and oxidative polycondensation ;O. I. Negru, M. Grigoras • The 13th International Balkan Workshop on Applied Physics and Materials Science”, Constanta, 4-6 iulie 2013 • A comparative study of optical and electronic properties of arylenevinylene and aryleneethynylene polymers containing 2,7 and 3,6 disubstitutedcarbazole units; A. M. Catargiu, M Grigoras