Vibronic exciton model for low bandgap donor–acceptor polymers

Balooch Qarai, Mohammad; Chang, Xin; Spano, F. C.

doi:10.1063/5.0029193

Vibronic exciton model for low bandgap donor–acceptor polymers

Journal Article · Tue Dec 22 00:00:00 EST 2020 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0029193· OSTI ID:1853426

^[1]; Chang, Xin ^[2]; ^[2]

Temple Univ., Philadelphia, PA (United States); Temple Univ., Philadelphia, PA (United States)
Temple Univ., Philadelphia, PA (United States)

In this study, a vibronic exciton model is introduced to describe the excited state band structure and associated absorption spectra of low bandgap donor–acceptor conjugated polymers. The Hamiltonian is represented in a diabatic basis consisting of Frenkel-like donor and acceptor fragment excitations as well as charge-transfer (CT) excitations between neighboring fragments. States are coupled to each other through electron and hole transfer as well as Coulombically, through interacting fragment transition dipole moments. Local vibronic coupling involving the prominent aromatic-quinoidal vibrational mode, which is responsible for pronounced vibronic progressions in most conjugated oligomers and polymers, is also included. The DAD repeat unit is shown to behave like a J-aggregate trimer, driven by both the sizable in-phase electron and hole transfer integrals between donor and acceptor fragments as well as negative Coulomb coupling between donor and acceptor fragment excitations. The J-aggregate behavior is enhanced in the polymer limit through inter-repeat unit coupling, with the 0–0 vibronic peak significantly enhanced in the lowest-energy near-IR band. In addition, the radiative rate is enhanced by the number of coherently connected repeat units. The near-IR band is shown to possess roughly equal admixtures of CT and Frenkel-like excitations. Applications are made to the polymer PffBT4T-2DT, with the simulated absorption spectrum quantitatively capturing the salient features of the measured spectrum.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Washington, Seattle, WA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: SC0020046

OSTI ID:: 1853426

Alternate ID(s):: OSTI ID: 1737840

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 24 Vol. 153; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (73)

Low Band-Gap Conjugated Polymers with Strong Interchain Aggregation and Very High Hole Mobility Towards Highly Efficient Thick-Film Polymer Solar Cells Chen, Zhenhui; Cai, Ping; Chen, Junwu Advanced Materials, Vol. 26, Issue 16 https://doi.org/10.1002/adma.201305092	journal	February 2014
2,1,3-Benzothiadiazole-5,6-Dicarboxylic Imide - A Versatile Building Block for Additive- and Annealing-Free Processing of Organic Solar Cells with Efficiencies Exceeding 8% Nielsen, Christian B.; Ashraf, Raja Shahid; Treat, Neil D. Advanced Materials, Vol. 27, Issue 5 https://doi.org/10.1002/adma.201404858	journal	December 2014
Diketopyrrolopyrroles: Synthesis, Reactivity, and Optical Properties Grzybowski, Marek; Gryko, Daniel T. Advanced Optical Materials, Vol. 3, Issue 3 https://doi.org/10.1002/adom.201400559	journal	January 2015
π-Conjugated Donor Polymers: Structure Formation and Morphology in Solution, Bulk and Photovoltaic Blends Hildner, Richard; Köhler, Anna; Müller-Buschbaum, Peter Advanced Energy Materials, Vol. 7, Issue 16 https://doi.org/10.1002/aenm.201700314	journal	August 2017
Effects of alkyl side chain and electron-withdrawing group on benzo[1,2,5]thiadiazole–thiophene-based small molecules in organic photovoltaic cells Cho, Ara; Song, Chang Eun; Lee, Sang Kyu Journal of Materials Science, Vol. 51, Issue 14 https://doi.org/10.1007/s10853-016-9964-x	journal	April 2016
The near ultraviolet spectra of 2,1,3-benzothiadiazole and its deuterated and substituted derivatives Gordon, R. D.; Yang, R. F. Journal of Molecular Spectroscopy, Vol. 39, Issue 2 https://doi.org/10.1016/0022-2852(71)90061-0	journal	August 1971
Studies of the electronic absorption and emission spectra of 2,1,3-benzothiadiazole Henry, Bryan R.; Morrison, James D. Journal of Molecular Spectroscopy, Vol. 55, Issue 1-3 https://doi.org/10.1016/0022-2852(75)90271-4	journal	March 1975
Determining the spatial coherence of excitons from the photoluminescence spectrum in charge-transfer J-aggregates Hestand, Nicholas J.; Spano, Frank C. Chemical Physics, Vol. 481 https://doi.org/10.1016/j.chemphys.2016.06.005	journal	December 2016
How the structural deviations on the backbone of conjugated polymers influence their optoelectronic properties and photovoltaic performance Chochos, Christos L.; Choulis, Stelios A. Progress in Polymer Science, Vol. 36, Issue 10 https://doi.org/10.1016/j.progpolymsci.2011.04.003	journal	October 2011
Recent advances in high performance donor-acceptor polymers for organic photovoltaics Holliday, Sarah; Li, Yilin; Luscombe, Christine K. Progress in Polymer Science, Vol. 70 https://doi.org/10.1016/j.progpolymsci.2017.03.003	journal	July 2017
The synthesis and examination of spectral properties of some 2,2′-bithienyl derivatives with carbonyl-containing substituents Lukeš, Vladimír; Danko, Martin; Andicsová, Anita Synthetic Metals, Vol. 165 https://doi.org/10.1016/j.synthmet.2012.12.021	journal	February 2013
Vibronic structure of PTCDA stacks: the exciton–phonon-charge-transfer dimer Hennessy, M. H.; Soos, Z. G.; Pascal, R. A. Chemical Physics, Vol. 245, Issue 1-3 https://doi.org/10.1016/s0301-0104(99)00082-8	journal	July 1999
Molecular Aggregate Photophysics beyond the Kasha Model: Novel Design Principles for Organic Materials Hestand, Nicholas J.; Spano, Frank C. Accounts of Chemical Research, Vol. 50, Issue 2 https://doi.org/10.1021/acs.accounts.6b00576	journal	January 2017
Recent Advances in Bulk Heterojunction Polymer Solar Cells Lu, Luyao; Zheng, Tianyue; Wu, Qinghe Chemical Reviews, Vol. 115, Issue 23 https://doi.org/10.1021/acs.chemrev.5b00098	journal	August 2015
Low-Bandgap Near-IR Conjugated Polymers/Molecules for Organic Electronics Dou, Letian; Liu, Yongsheng; Hong, Ziruo Chemical Reviews, Vol. 115, Issue 23 https://doi.org/10.1021/acs.chemrev.5b00165	journal	August 2015
Expanded Theory of H- and J-Molecular Aggregates: The Effects of Vibronic Coupling and Intermolecular Charge Transfer Hestand, Nicholas J.; Spano, Frank C. Chemical Reviews, Vol. 118, Issue 15 https://doi.org/10.1021/acs.chemrev.7b00581	journal	April 2018
Analyses of Thiophene-Based Donor–Acceptor Semiconducting Polymers toward Designing Optical and Conductive Properties: A Theoretical Perspective Matsui, Toru; Imamura, Yutaka; Osaka, Itaru The Journal of Physical Chemistry C, Vol. 120, Issue 15 https://doi.org/10.1021/acs.jpcc.5b05794	journal	April 2016
Put Your Backbone into It: Excited-State Structural Relaxation of PffBT4T-2DT Conducting Polymer in Solution Dantanarayana, Varuni; Fuzell, Jack; Nai, Dingqi The Journal of Physical Chemistry C, Vol. 122, Issue 12 https://doi.org/10.1021/acs.jpcc.8b01356	journal	February 2018
Multiphoton Microscopy of π-Conjugated Copolymers and Copolymer/Fullerene Blends for Organic Photovoltaic Applications Vardeny, Shai R.; Baniya, Sangita; Cromey, Benjamin ACS Applied Materials & Interfaces, Vol. 10, Issue 37 https://doi.org/10.1021/acsami.8b11378	journal	August 2018
Oligoselenophene Derivatives Functionalized with a Diketopyrrolopyrrole Core for Molecular Bulk Heterojunction Solar Cells Mazzio, Katherine A.; Yuan, Mingjian; Okamoto, Ken ACS Applied Materials & Interfaces, Vol. 3, Issue 2 https://doi.org/10.1021/am100920s	journal	January 2011
The Spectral Signatures of Frenkel Polarons in H- and J-Aggregates Spano, Frank C. Accounts of Chemical Research, Vol. 43, Issue 3 https://doi.org/10.1021/ar900233v	journal	March 2010
Processable Low-Bandgap Polymers for Photovoltaic Applications ^† Boudreault, Pierre-Luc T.; Najari, Ahmed; Leclerc, Mario Chemistry of Materials, Vol. 23, Issue 3 https://doi.org/10.1021/cm1021855	journal	February 2011
Indacenodithiophene Semiconducting Polymers for High-Performance, Air-Stable Transistors Zhang, Weimin; Smith, Jeremy; Watkins, Scott E. Journal of the American Chemical Society, Vol. 132, Issue 33 https://doi.org/10.1021/ja1049324	journal	August 2010
Vibronic Coupling in J-Aggregates and Beyond: A Direct Means of Determining the Exciton Coherence Length from the Photoluminescence Spectrum Spano, Frank C.; Yamagata, Hajime The Journal of Physical Chemistry B, Vol. 115, Issue 18 https://doi.org/10.1021/jp104752k	journal	May 2011
Twist Angle Plays an Important Role in Photophysical Properties of a Donor–Acceptor-Type Conjugated Polymer: A Combined Ensemble and Single-Molecule Study Habuchi, Satoshi; Fujita, Hiroyuki; Michinobu, Tsuyoshi The Journal of Physical Chemistry B, Vol. 115, Issue 49 https://doi.org/10.1021/jp209405k	journal	December 2011
Breaking Down the Problem: Optical Transitions, Electronic Structure, and Photoconductivity in Conjugated Polymer PCDTBT and in Its Separate Building Blocks Banerji, Natalie; Gagnon, Eric; Morgantini, Pierre-Yves The Journal of Physical Chemistry C, Vol. 116, Issue 21 https://doi.org/10.1021/jp301639e	journal	May 2012
Optical Properties of Oligothiophene Substituted Diketopyrrolopyrrole Derivatives in the Solid Phase: Joint J- and H-Type Aggregation Kirkus, Mindaugas; Wang, Linjun; Mothy, Sébastien The Journal of Physical Chemistry A, Vol. 116, Issue 30 https://doi.org/10.1021/jp305097q	journal	July 2012
A Benchmark of Excitonic Couplings Derived from Atomic Transition Charges Kistler, Kurt A.; Spano, Francis C.; Matsika, Spiridoula The Journal of Physical Chemistry B, Vol. 117, Issue 7 https://doi.org/10.1021/jp310603z	journal	February 2013
HJ-Aggregate Behavior of Crystalline 7,8,15,16-Tetraazaterrylene: Introducing a New Design Paradigm for Organic Materials Yamagata, H.; Maxwell, D. S.; Fan, J. The Journal of Physical Chemistry C, Vol. 118, Issue 49 https://doi.org/10.1021/jp509011u	journal	November 2014
J-Aggregate Behavior in Poly-3-hexylthiophene Nanofibers Niles, Edwards T.; Roehling, John D.; Yamagata, Hajime The Journal of Physical Chemistry Letters, Vol. 3, Issue 2 https://doi.org/10.1021/jz201509h	journal	January 2012
Strong Photophysical Similarities between Conjugated Polymers and J-aggregates Yamagata, Hajime; Spano, Frank C. The Journal of Physical Chemistry Letters, Vol. 5, Issue 3 https://doi.org/10.1021/jz402450m	journal	January 2014
Synthesis and Characterization of Thiophene-Containing Naphthalene Diimide n-Type Copolymers for OFET Applications Durban, Matthew M.; Kazarinoff, Peter D.; Luscombe, Christine K. Macromolecules, Vol. 43, Issue 15 https://doi.org/10.1021/ma100997g	journal	August 2010
Donor–Acceptor Copolymers of Relevance for Organic Photovoltaics: A Theoretical Investigation of the Impact of Chemical Structure Modifications on the Electronic and Optical Properties Pandey, Laxman; Risko, Chad; Norton, Joseph E. Macromolecules, Vol. 45, Issue 16 https://doi.org/10.1021/ma301164e	journal	July 2012
Segregated versus Mixed Interchain Stacking in Highly Oriented Films of Naphthalene Diimide Bithiophene Copolymers Brinkmann, Martin; Gonthier, Eric; Bogen, Stéfan ACS Nano, Vol. 6, Issue 11 https://doi.org/10.1021/nn304213h	journal	October 2012
Tracking the coherent generation of polaron pairs in conjugated polymers De Sio, Antonietta; Troiani, Filippo; Maiuri, Margherita Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13742	journal	December 2016
Direct observation of ultrafast long-range charge separation at polymer–fullerene heterojunctions Provencher, Françoise; Bérubé, Nicolas; Parker, Anthony W. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5288	journal	July 2014
Aggregation and morphology control enables multiple cases of high-efficiency polymer solar cells Liu, Yuhang; Zhao, Jingbo; Li, Zhengke Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6293	journal	November 2014
Impact of polymorphism on the optoelectronic properties of a low-bandgap semiconducting polymer Li, Mengmeng; Balawi, Ahmed Hesham; Leenaers, Pieter J. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-10519-z	journal	June 2019
Intrinsically distinct hole and electron transport in conjugated polymers controlled by intra and intermolecular interactions Pace, Giuseppina; Bargigia, Ilaria; Noh, Yong-Young Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-13155-9	journal	November 2019
A stable solution-processed polymer semiconductor with record high-mobility for printed transistors Li, Jun; Zhao, Yan; Tan, Huei Shuan Scientific Reports, Vol. 2, Issue 1 https://doi.org/10.1038/srep00754	journal	October 2012
A quantum-chemical perspective into low optical-gap polymers for highly-efficient organic solar cells Risko, Chad; McGehee, Michael D.; Brédas, Jean-Luc Chem. Sci., Vol. 2, Issue 7 https://doi.org/10.1039/c0sc00642d	journal	January 2011
High mobility diketopyrrolopyrrole (DPP)-based organic semiconductor materials for organic thin film transistors and photovoltaics Li, Yuning; Sonar, Prashant; Murphy, Leanne Energy & Environmental Science, Vol. 6, Issue 6 https://doi.org/10.1039/c3ee00015j	journal	January 2013
Sub-picosecond delocalization in the excited state of conjugated homopolymers and donor–acceptor copolymers Banerji, Natalie Journal of Materials Chemistry C, Vol. 1, Issue 18 https://doi.org/10.1039/c3tc00005b	journal	January 2013
Small molecules incorporating regioregular oligothiophenes and fluorinated benzothiadiazole groups for solution-processed organic solar cells Yuan, Liu; Zhao, Yifan; Lu, Kun J. Mater. Chem. C, Vol. 2, Issue 29 https://doi.org/10.1039/c4tc00921e	journal	January 2014
Natures of optical absorption transitions and excitation energy dependent photostability of diketopyrrolopyrrole (DPP)-based photovoltaic copolymers Wood, Sebastian; Wade, Jessica; Shahid, Munazza Energy & Environmental Science, Vol. 8, Issue 11 https://doi.org/10.1039/c5ee01974e	journal	January 2015
Super-exchange-induced high performance charge transport in donor–acceptor copolymers Cheng, Changli; Geng, Hua; Yi, Yuanping Journal of Materials Chemistry C, Vol. 5, Issue 13 https://doi.org/10.1039/c6tc05534f	journal	January 2017
Evolving molecular architectures of donor–acceptor conjugated polymers for photovoltaic applications: from one-dimensional to branched to two-dimensional structures Su, Yu-Wei; Lin, Yu-Che; Wei, Kung-Hwa Journal of Materials Chemistry A, Vol. 5, Issue 46 https://doi.org/10.1039/c7ta07228g	journal	January 2017
Vibronic relaxation energies of acene-related molecules upon excitation or ionization Andrzejak, Marcin; Petelenz, Piotr Physical Chemistry Chemical Physics, Vol. 20, Issue 20 https://doi.org/10.1039/c8cp01562g	journal	January 2018
Effect of donor length on electronic structures and charge transport polarity for DTDPP-based D–A copolymers: a computational study based on a super-exchange model He, Feifei; Cheng, Changli; Geng, Hua Journal of Materials Chemistry A, Vol. 6, Issue 25 https://doi.org/10.1039/c8ta02175a	journal	January 2018
Increased charge carrier mobility and molecular packing of a solution sheared diketopyrrolopyrrole-based donor–acceptor copolymer by alkyl side chain modification Hambsch, Mike; Erdmann, Tim; Chew, Annabel R. Journal of Materials Chemistry C, Vol. 7, Issue 12 https://doi.org/10.1039/c8tc06255b	journal	January 2019
The effect of alkyl side chain length on the formation of two semi-crystalline phases in low band gap conjugated polymers Li, Mengmeng; Leenaers, Pieter J.; Wienk, Martijn M. Journal of Materials Chemistry C, Vol. 8, Issue 17 https://doi.org/10.1039/d0tc00172d	journal	January 2020
Enhancement of Phosphorescence Ability upon Aggregation of Dye Molecules McRae, Eion G.; Kasha, Michael The Journal of Chemical Physics, Vol. 28, Issue 4 https://doi.org/10.1063/1.1744225	journal	April 1958
Exciton transfer integrals between polymer chains Barford, William The Journal of Chemical Physics, Vol. 126, Issue 13 https://doi.org/10.1063/1.2714516	journal	April 2007
Excitonic versus electronic couplings in molecular assemblies: The importance of non-nearest neighbor interactions Gierschner, Johannes; Huang, Ya-Shih; Van Averbeke, Bernard The Journal of Chemical Physics, Vol. 130, Issue 4 https://doi.org/10.1063/1.3065267	journal	January 2009
Tuning the electronic coupling in a low-bandgap donor–acceptor copolymer via the placement of side-chains Oberhumer, Philipp M.; Huang, Ya-Shih; Massip, Sylvain The Journal of Chemical Physics, Vol. 134, Issue 11 https://doi.org/10.1063/1.3562936	journal	March 2011
Vibronic coupling in quantum wires: Applications to polydiacetylene Yamagata, H.; Spano, F. C. The Journal of Chemical Physics, Vol. 135, Issue 5 https://doi.org/10.1063/1.3617432	journal	August 2011
Monopole effects on electronic excitation interactions between large molecules. I. Application to energy transfer in chlorophylls Chang, Jane C. The Journal of Chemical Physics, Vol. 67, Issue 9 https://doi.org/10.1063/1.435427	journal	January 1999
Excitation shifts of parallel conjugated polymers due to π‐electron dispersion forces Soos, Z. G.; Hayden, G. W.; McWilliams, P. C. M. The Journal of Chemical Physics, Vol. 93, Issue 10 https://doi.org/10.1063/1.459715	journal	November 1990
The vibronic structure of the S ₀ ↔ S ₁ and S ₀ ↔ S ₂ transitions in simple oligomers of thiophene Negri, Fabrizia; Zgierski, Marek Z. The Journal of Chemical Physics, Vol. 100, Issue 4 https://doi.org/10.1063/1.466504	journal	February 1994
Interplay between intrachain and interchain interactions in semiconducting polymer assemblies: The HJ-aggregate model Yamagata, H.; Spano, F. C. The Journal of Chemical Physics, Vol. 136, Issue 18 https://doi.org/10.1063/1.4705272	journal	May 2012
Absorption and spontaneous emission in aggregates of conjugated polymers Manas, Eric S.; Spano, Frank C. The Journal of Chemical Physics, Vol. 109, Issue 18 https://doi.org/10.1063/1.477457	journal	November 1998
Interchain interactions in conjugated materials: The exciton model versus the supermolecular approach Beljonne, D.; Cornil, J.; Silbey, R. The Journal of Chemical Physics, Vol. 112, Issue 10 https://doi.org/10.1063/1.481031	journal	March 2000
The red-phase of poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV): A disordered HJ-aggregate Yamagata, Hajime; Hestand, Nicholas J.; Spano, Frank C. The Journal of Chemical Physics, Vol. 139, Issue 11 https://doi.org/10.1063/1.4819906	journal	September 2013
Interference between Coulombic and CT-mediated couplings in molecular aggregates: H- to J-aggregate transformation in perylene-based π-stacks Hestand, Nicholas J.; Spano, Frank C. The Journal of Chemical Physics, Vol. 143, Issue 24 https://doi.org/10.1063/1.4938012	journal	December 2015
Atomic and electronic structure of polymer organic semiconductors: P3HT, PQT, and PBTTT Northrup, John E. Physical Review B, Vol. 76, Issue 24 https://doi.org/10.1103/physrevb.76.245202	journal	December 2007
Crystallochromy of perylene pigments: Influence of an enlarged polyaromatic core region Gisslén, L.; Scholz, R. Physical Review B, Vol. 83, Issue 15 https://doi.org/10.1103/physrevb.83.155311	journal	April 2011
Theory of Primary Photoexcitations in Donor-Acceptor Copolymers Aryanpour, Karan; Dutta, Tirthankar; Huynh, Uyen N. V. Physical Review Letters, Vol. 115, Issue 26 https://doi.org/10.1103/physrevlett.115.267401	journal	December 2015
Band to correlated crossover in alternating Hubbard and Pariser-Parr-Pople chains: Nature of the lowest singlet excitation of conjugated polymers Soos, Z. G.; Ramasesha, S.; Galvão, D. S. Physical Review Letters, Vol. 71, Issue 10 https://doi.org/10.1103/physrevlett.71.1609	journal	September 1993
Role of Intermolecular Coupling in the Photophysics of Disordered Organic Semiconductors: Aggregate Emission in Regioregular Polythiophene Clark, Jenny; Silva, Carlos; Friend, Richard H. Physical Review Letters, Vol. 98, Issue 20 https://doi.org/10.1103/physrevlett.98.206406	journal	May 2007
Electronic and vibrational spectroscopy studies of PffBT4T π-conjugated donor–acceptor copolymer Vardeny, Shai R.; Baniya, Sangita; Lafalce, Evan Journal of Photonics for Energy, Vol. 8, Issue 03 https://doi.org/10.1117/1.jpe.8.032203	journal	March 2018
Organic and solution-processed tandem solar cells with 17.3% efficiency Meng, Lingxian; Zhang, Yamin; Wan, Xiangjian Science, Vol. 361, Issue 6407 https://doi.org/10.1126/science.aat2612	journal	August 2018
H- and J-Aggregate Behavior in Polymeric Semiconductors Spano, Frank C.; Silva, Carlos Annual Review of Physical Chemistry, Vol. 65, Issue 1 https://doi.org/10.1146/annurev-physchem-040513-103639	journal	April 2014
Energy Transfer Mechanisms and the Molecular Exciton Model for Molecular Aggregates Kasha, Michael Radiation Research, Vol. 20, Issue 1 https://doi.org/10.2307/3571331	journal	September 1963

Similar Records

HJ-aggregates of donor–acceptor–donor oligomers and polymers

Journal Article · Sun Jul 18 20:00:00 EDT 2021 · Journal of Chemical Physics · OSTI ID:1853427

Electronic and vibronic properties of a discotic liquid-crystal and its charge transfer complex

Journal Article · Mon Jan 06 23:00:00 EST 2014 · Journal of Chemical Physics · OSTI ID:22254171

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
absorption spectroscopy
energetics and spatio-temporal dynamics
excitons
polymers
vibronic transitions

Vibronic exciton model for low bandgap donor–acceptor polymers

Citation Formats

References (73)

Similar Records

Related Subjects