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. Mircea Grigoras
Petru Poni Institute of Macromolecular Chemistry - Iasi,
Institute of Excellence of the Romanian Academy
Tel.: +40-0232-260332/117 E-mail: grim@icmpp.ro
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Summary
Research team
Objectives
Project value
• Project stage: -Phase 2012
-Phase 2013
-Phase 2014
• Results dissemination
Articles
Participation on different symposia
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.
Research team
Project manager
 Dr. Mircea Grigoras
Dr. Anca Stanculescu
Dr. Loredana Vacareanu
Dr. Marcela Socol
Dr. Ana-Maria Catargiu
Dr. Teofilia Ivan
Drd. Oana-Iuliana Negru
Asit. Oltica Tescu
Objectives
The general objective of 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
Project value
Stage 2012: 550000 lei
Stage 2013: 225745,43 lei
Stage 2014: 225000 lei
Stage 2015: lei
Total Budget: 1500000 lei
Project stage: Phase 2012
Objectives:
1. Synthesis of new monomers based on carbazole as 2,7- disubtituted
ring and to use in synthesis of polyarylenes and polyarylenevinylenes
2. The synthesis of polymers in different conditions, their
characterization and optoelectronic properties (UV-Vis,fluorescence
spectra and electrochemical behavior [HOMO, LUMO levels, Eg]
3. Synthesis of oligomers and dendrimers based on triphenylamine and
benzene by Suzuki, Wittig or Heck reaction and their chemical
characterization.
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 additionfragmentation chain transfer polymerization (RAFT); M.Grigoras, O. I. Negru,
Polymers,). Doi: 10.3390/polym4021183; www.mdpi.com/journal/polymers,
publish in : 4(2), 1183-1194, (2012). FI (2012) =1.687.
3. Synthesis and optoelectronic characterization of some star-shaped oligomers with
benzene and triphenylamine cores , T. Ivan, L.Vacareanu, M.Grigoras, ISRN
Organic Chemistry, DOI:10.5402/2012/976178, article ID 976178, 11 pages,
(2012). FI (2012) = 1.
4. 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, early view:
http:/dx.doi.org/10.1016/j.dyepig.2013.01.025, Publish: 98, 71-81 (2013). FI
(2012)= 3.532.
5. Synthesis and photophysical properties of two intramolecular chharge-tranfer
chromophores obtained by [2+2] cycloaddition of TCNE and TCNQ to an electron
rich alkyne, T. Ivan, L.Vacareanu, M.Grigoras, Revue de Chimie, publish in :64(4),
372-377, (2013). FI (2012) = 0.538.
6. Linear and Hyperbranched triphnylamine-based polyarylenevinylenes: A comparative
optoelectronic study, T. Ivan, L.Vacareanu, M.Grigoras, Design Monomers and
Polymers, early view:http://dx.doi.org/10.1080/15685551.2013.840495, 17(2), 156165, (2014). FI (2012) = 0.875.
7. 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, publish in :58 (2-3), 113-119, (2013) . FI (2012) = 0.331.
8. 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 Nanotechnologies 8411,
84111G1-G10, doi:10.1117/12.974919, (2012).
PhD Thesis
Synthesis of new fluorescent arylamine
oligomers and polymers -drd. Teofilia Ivan, PhD
1.
superviser Dr. Mircea Grigoras-graduated in November
2012).
Participation on different symposia 2012
Communications
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 Coordination and
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,
Posters
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 MaterialsSzeged- 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 postmodification reactions, T. Ivan, A. M Catargiu, L. Văcăreanu, M. Grigoraş
Project stage: Phase 2013
Objectives:
1. Synthesis and characterization of new conjugated oligomers and polymers
with donor groups.
2. Synthesis of photoactive films of conjugated oligomers and polymers
with donor grups and small molecular acceptors.
Results dissemination 2013
Articles
1.
2.
3.
4.
Grafted Polytriphenylamines Synthesized by Tandem Atom Transfer Radical Polymerization
and Oxidative Polycondensation, Oana Iuliana Negru, Mircea Grigoras, Iranian Polymer
Journal, early view: DOI 101007/s13726-013-0163-1, publish in: 22(9), 641-651, (2013). FI
(2012) = 1.053.
Polytripenylamine synthesized by interfacial and microemulsion oxidative polymerization,
Oana Iuliana Negru, Mircea Grigoras, Colloid and Polymer Science,early view:
10.1007/s00396-013-3055-1, publish in: 292, 143-151, (2014). 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, Radu Tigoianu, Journal of Luminescence; early view DOI:
10.1016/j.jlumin.2014.02.032 Publish in:153, 5-11, (2014). FI (2013) = 2.367.
Laser prepared organic heterostructures based on star –shaped arilenevinylene compounds,
Anca Stanculescu, Gabriel Socol, Mircea Grigoras, Teofilia Ivan, Loredana Vacareanu,
Marcela Socol, Oana Rosoga, Ion N. Mihailescu Carmen Breazu, Iuliana Iordache, Nicoleta
Preda, Florin Stanculescu, Applied Physics A: Material Science and Processing, early view :
DOI 10.1007/s00339-014-8521-1, publish in :117, 261-268, (2014). FI(2013)= 1.694
5.
Tuning optical and electronic properties of poly(4,4’-triphenylaminvinylene)s by postmodification reactions, Dyes and Pigments, Mircea Grigoras, Ana Maria Catargiu,Teofilia Ivan,
Loredana Vacareanu, Boris Minaev, Evgeniy Stromylo, early view DOI:
10.1016/j.dyepig.2014.08.016, publish in: 113, 227-238, (2015). FI (2013) = 3.468.
6. A comparative study of optical and electronic properties of arylenevinylene and aryleneethynylene
polymers containing 2,7 and 3,6 disubstituted carbazole units, Ana-Maria Catargiu, Mircea
Grigoras, Revue Romaine de Chimie, submitted for publication. FI (2013) = 0.393.
PhD Thesis
Studies on the synthesis of polymers with
chromophore groups by controlled radical
polymerization-drd. Oana Iuliana Irimia (Negru),
PhD superviser Dr. Mircea Grigoras-graduated in
October 2013).
Participation on different symposia 2013
Communications
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 ;AnaMaria 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 carbazole units :Loredana Vacareanu ,
Ana-Maria Catargiu and Mircea Grigoras.,
Posters
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 disubstituted carbazole units; A. M.
Catargiu, M Grigoras
 The 12 th International Conference on Laser Ablation (COLA
2013), Ischia, Italia, 6-11 Octombrie 2013
 Laser prepared organic heterostructures based on star –shaped arylenevynilene compounds,
Anca Stanculescu, Gabriel Socol, Mircea Grigoras, Teofilia Ivan, Loredana Vacareanu,
Marcela Socol, Oana Rosoga, Ion N. Mihailescu, Carmen Breazu, Nicoleta Preda, Florin
Stanculescu
Project stage: Phase 2014
Objectives:
1. Synthesis and characterization of new conjugated oligomers and polymers
with donor groups.
2. Synthesis of photoactive films of conjugated oligomers and polymers with
donor groups and small molecular acceptors.
Results dissemination 2014
Articles
1. Electrogenerated networks from poly [4-(diphenylamino)benzyl methacrylate] and their electrochromic
properties, Oana Iuliana Negru, Loredana Vacareanu, Mircea Grigoras, eXPRESS Polymer Letters ,
early view: DOI:10.3144/expresspolymlett.2014.68 , publish in : 8(9), 647-658, (2014). FI
(2013)=2.953.
2. Oligostyrene grafted poly(4,4’-triphenylamine vinylene)s obtained by combination of ATRP and SuzukiHeck reactions, Oana Iuliana Negru, Mircea Grigoras, Revue Romaine de Chimie, accepted for
publication in september 2014. FI (2013)= 0.393.
3. Spectroelectrochemical characterizations of isomeric conjugated polymers containig 2,7 and 3,6
carbazole linked by vinylene and ethynylene segments, Loredana Vacareanu, Ana Maria Catargiu,
Mircea Grigoras, Higt Performace Polymers , early view: DOI: 10.1177/095400831455529, accepted
for publication in september 2014. FI (2013)=1.09.
4. Poly(triphenilamine-vinylene) s bearing ethynylene side groups: synthesis by post-modification and
spetcroelectrochemical characterization; Loredana Vacareanu, Teofilia Ivan (Virag), Mircea Grigoras,
Journal of Applied Polymer Science, submitted for publication in july 2014. FI (2013)=1.64.
5. MAPLE prepared heterostructures with arylene based polymer active layer for photovoltaic
applications; Anca Stanculescu, Loredana Vacareanu, Florin Stanculescu, Gabriel Socol, Ana-Maria
Catargiu, Marcela Socol, Oana Rosoga, Carmen Breazu, Nicoleta Preda, Applied Surface Science
,submitted for publication in july 2014. FI (2013)=2.538.
6. Electrochemically generated networks from poly(4,4’-triphenylamine-co-9,9-dioctyl-2,7-
fluorene) with grafts containing carbazole groups, Oana Iuliana Negru, Mircea Grigoras,
Journal Polymer Research, submitted for publication in september 2014. FI (2013)=1.897.
7. Direct synthesis of bisbromine –functionalized indolo [3,2-b]carbazoles, Oana Iuliana
Negru, Mircea Grigoras, Letters in Organic Chemistry, submitted for publication in september
2014. FI (2013)= 0.648.
Participation on different symposia 2014
Communications
The 7th Edition of the International Conference: Advanced Topics in Optoelectronics,
Microelectronics and Nanotechnologies, Constanta, 21-24 August 2014
 New conjugated polymers based on 3,6- and 2,7- carbazole linked by phenylene ethynylene
segments for optoelectronic applications; Ana-Maria Catargiu and Mircea Grigoras
A XXXIII-a Conferinta Nationala de Chimie, cu participare internationala, Caciulata,
1-3 Octombrie 2014
 Spectroelectrochemical properties of the electrodeposited triphenylamine based polymers; Loredana
Vacareanu, Teofilia Ivan (Virag), Mircea Grigoras
"Alexandru Ioan Cuza" University Days, Faculty of Chemistry Conference, Iasi 31
Octombrie- 1 Noiembrie 2014
 Syntheisis and characterization of poly(aryleneethynylene)s containing indol[3,2-b]carbazole
moieties, Oana Iuliana Negru, Ana-Maria Catargiu, Mircea Grigoras
Posters
 E-MRS Spring Meeting, Lille, Franta, 25-31 Mai 2014
 MAPLE prepared heterostructures with arylene vinylene polymer :fullerene active layer for
phovoltaic applications ; Anca Stanculescu, Gabriel Socol, Ana-Maria Catargiu, Loredana Vacareanu,
Marcela Socol, Oana Rosoga, Carmen Breazu, Nicoleta Preda, Florin Stanculescu.
International Conference on Synthetic Materials ICSM 2014, Turku, Finlanda, 30
Iunie-5 Iulie 2014
 Electricalproperties of arylenevinylene based organic heterostructures, Florin Stanculescu, Marcela
Socol, Gabriel Socol, IN Mihailescu, Mircea Grigoras, Loredana Vacareanu, Oana Rosoga, Carmen
Breazu, Anca Stanculescu
The 7th Edition of the International Conference: Advanced Topics in Optoelectronics,
Microelectronics and Nanotechnologies, Constanta, 21-24 August 2014
 Electrogenerated network from poly(triphenylanime-co-9,9 –dioctyl -2,7 –fluorene) with grafted side
chains containing carbazole groups; Oana Iuliana Negru, Mircea Grigoras
5th International Symposium on Transparent Conductor Materials, TCM 2014, Creta,
Grecia, 12-17 Octombrie 2014
 Organic flexible heterostructures with Al:ZnO transparent conductor electrode for photovolataic
applications; Anca Stanculescu, Gabriel Socol, Loredana Vacareanu, Marcela Socol, Oana Rosoga,
Carmen Breazu, M. Girtan, Florin Stanculescu
The 2nd CEEPN WORKSHOP ON POLYMER SCIENCE , Iasi, 24-26 Octombrie
2014
Photophysical properties of a series of oligomers with vinylene, imine, azine and ethynylene
spacers bearing triphenylamine moiety; B. Mineaev, E Stromylo, Mircea Grigoras, Loredana
Vacareanu
Post–modification poly(triphenylamine-vinylene)s a way to tune their optical and electronic
properties; Loredana Vacareanu, Ana-Maria Catargiu, Mircea Grigoras, ; B. Mineaev, E
Stromylo,