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Photovoltaic studies on perylene diimide-based

copolymers containing electronic push–pull
Cite this: RSC Advances, 2013, 3,
5108 chromophores3
Published on 05 February 2013 on http://pubs.rsc.org | doi:10.1039/C3RA23383A

Michael Ruby Raj, Sekar Ramkumar and Sambandam Anandan*

Downloaded by Nanyang Technological University on 19 March 2013

Received 18th December 2012,
Accepted 31st January 2013
DOI: 10.1039/c3ra23383a
www.rsc.org/advances
Soluble perylene diimide-based copolymers with conjugated electronic push–pull substituent species
(piperidinyl and 4-tert-butylphenoxyl) on the 1,7-bay position of the perylene core and a 5,59-bis(4-
aminophenyl)-2-29-bifuryl as terminal group were synthesized and characterized in order to fabricate bulk
heterojunction solar cells. The introduction of such electronic push–pull substituents, which results in
relatively low-lying HOMO and high-lying LUMO energy levels, was achieved experimentally using
absorption and cyclic voltammetric measurements and also by density functional theory. Successfully fine-
tuned HOMO and LUMO energy levels translated into a high open circuit voltage (Voc > 1.0 V) in fabricated
photovoltaic devices of type ITO/PEDOT:PSS/rr-P3HT:Perylene diimide-based copolymers/Ca/Al. However,
a relatively poor fill factor and efficiency may be observed due to the large degree of aggregation
domains, which are observed from atomic force microscopic studies.

Introduction tems5 which exhibit broad absorption in the near-infrared

As the importance of renewable energy sources grows, the
development of highly efficient organic photovoltaic cells is
becoming of increasing relevance for electrical energy produc-
tion.1,2 For the construction of solar energy conversion
systems, many research efforts have been focused on the
exploration of molecular photoelectronic devices for applica-
tion in photochemical energy conversion, which requires the
design of light-harvesting and electron transporting capacity
bichromophoric and multichromophoric systems that
undergo photoinduced intramolecular charge transfer pro-
cesses.3 For this purpose, recent developments in the field of
organic photovoltaics have boosted great interest in the
development of a new class of photofunctional materials and
multifunctional organic dyes or pigments exhibiting broad
light-harvesting properties in the near-infrared (NIR) region,
which is highly desirable to attain efficient solar energy
conversion processes.1,4 In this regard, recent synthetic
strategies have been developed for design and synthesis of
efficient light harvesting materials based on electronic push–
pull p-conjugated systems combined with an electron donor–
acceptor pair, which lead to feasible photoinduced charge
generation in bichromophoric and multichromophoric sys-
Nanomaterials & Solar Energy Conversion Lab, Department of Chemistry, National
Institute of Technology, Tiruchirappalli-620 015, India. E-mail: sanand@nitt.edu;
sanand99@yahoo.com
3 Electronic supplementary information (ESI) available: 1H NMR spectrum of
compound 3,4,5 and 6, GPC curves, TGA curves and DFT data (XYZ coordinates)
of copolymers. See DOI: 10.1039/c3ra23383a
(NIR) region as one of the key components to construct high
performance solar cells.6–8 In addition to near-infrared (NIR)
light-harvesting capability, high photostability and thermal
durability,9 distinct redox properties,10 specific carrier injec-
tion-tuning properties,11 excellent electron acceptor ability,12 a
large molar extinction coefficient in the wavelength range of
480–550 nm13 and unity fluorescence quantum yields14 are
also key factors to attain efficient solar energy conversion
processes. Among the different functional materials avail-
able,15 researchers have made efforts to modify perylene
diimide based dyes with versatile functionalized electronic
push–pull groups at bay-positions, as well as at imide
positions, in order to utilize them as an active light-harvesting
component to construct bulk heterojunction polymer solar
cells.16 The main reason for introducing groups at bay
positions of the perylene diimide (PDI) core is to use an
electronic push–pull approach to enhance electron mobilities
via strong p–p stacking interactions between the planar PDI
moieties,17 and to induce an ultrafast photoinduced charge-
separated state which contributes to the slowing down of
charge recombination.18 However, the electronic structures of
perylene p-systems are not significantly affected upon intro-
duction of substituents at the imide position because the
frontier molecular orbital nodes are available on the imide
nitrogen atoms.10a,19,20
Recently, an alternating copolymer (PTCDI-PFDA) bearing a
non-bay substituted perylene moiety combined with a p-con-
jugated moiety (5,59-bis(4-aminophenyl)-2-29-bifuryl; PFDA)
moieties was prepared and utilized as an active electron

5108 | RSC Adv., 2013, 3, 5108–5120 This journal is ß The Royal Society of Chemistry 2013