Effect of polymerization statistics on the electronic properties of copolymers for organic photovoltaics
Effect of polymerization statistics on the electronic properties of copolymers for organic photovoltaics
Statistical block copolymers, composed of donor (D) and acceptor (A) blocks, are a novel type of material for organic photovoltaics (OPVs) devices. In particular a new series of polymers based on PBTZT-stat-BDTT-8, recently developed by Merck, offers high solubility in different solvents, and a high power conversion efficiency (PCE) in different device architectures. Although it is known that the electronic properties of these materials may be significantly affected by attaching different functional groups on different blocks, it is not fully clear how important the influence of the polymer composition (i.e., the D/A block ratio) is, even if previous studies suggest that this might also have an effect. Therefore, the effect of the polymer composition in terms of HOMO, LUMO energies, and band gap was explored by studying a number of long chain oligomers with more than 1000 atoms each and with different D/A ratios. This study, that is novel both conceptually and methodologically, was made possible by using the linear-scaling reformulation of DFT implemented in the ONETEP code. Our results showed that changing the composition has a significant effect on the electronic structure of statistical copolymers, making this an alternative and suitable strategy to obtain materials with desired properties. Also, a systematic analysis of the effect of a range of different substituents placed in the D and A blocks of PBTZT-stat-BDTT-8 was performed in order to investigate how this class of materials responds to functionalization. We found that it is not possible to know a priori using chemical intuition what kind of influence different types of functional groups may have on these systems, and therefore, computational modeling is essential.
1-10
Boschetto, Gabriele
4b29b31b-e76f-42fe-8b1f-b0556149fb32
Xue, Hong-Tao
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Dziedzic, Jacek
8e2fdb55-dade-4ae4-bf1f-a148a89e4383
Krompiec, Michal
c5280165-053d-422d-8872-ae612852d773
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
9 February 2017
Boschetto, Gabriele
4b29b31b-e76f-42fe-8b1f-b0556149fb32
Xue, Hong-Tao
784078a4-1b02-44eb-863b-ea5831e02585
Dziedzic, Jacek
8e2fdb55-dade-4ae4-bf1f-a148a89e4383
Krompiec, Michal
c5280165-053d-422d-8872-ae612852d773
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Boschetto, Gabriele, Xue, Hong-Tao, Dziedzic, Jacek, Krompiec, Michal and Skylaris, Chris-Kriton
(2017)
Effect of polymerization statistics on the electronic properties of copolymers for organic photovoltaics.
The Journal of Physical Chemistry C, .
(doi:10.1021/acs.jpcc.6b10851).
Abstract
Statistical block copolymers, composed of donor (D) and acceptor (A) blocks, are a novel type of material for organic photovoltaics (OPVs) devices. In particular a new series of polymers based on PBTZT-stat-BDTT-8, recently developed by Merck, offers high solubility in different solvents, and a high power conversion efficiency (PCE) in different device architectures. Although it is known that the electronic properties of these materials may be significantly affected by attaching different functional groups on different blocks, it is not fully clear how important the influence of the polymer composition (i.e., the D/A block ratio) is, even if previous studies suggest that this might also have an effect. Therefore, the effect of the polymer composition in terms of HOMO, LUMO energies, and band gap was explored by studying a number of long chain oligomers with more than 1000 atoms each and with different D/A ratios. This study, that is novel both conceptually and methodologically, was made possible by using the linear-scaling reformulation of DFT implemented in the ONETEP code. Our results showed that changing the composition has a significant effect on the electronic structure of statistical copolymers, making this an alternative and suitable strategy to obtain materials with desired properties. Also, a systematic analysis of the effect of a range of different substituents placed in the D and A blocks of PBTZT-stat-BDTT-8 was performed in order to investigate how this class of materials responds to functionalization. We found that it is not possible to know a priori using chemical intuition what kind of influence different types of functional groups may have on these systems, and therefore, computational modeling is essential.
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Accepted/In Press date: 19 January 2017
e-pub ahead of print date: 27 January 2017
Published date: 9 February 2017
Organisations:
Chemistry
Identifiers
Local EPrints ID: 405246
URI: http://eprints.soton.ac.uk/id/eprint/405246
ISSN: 1932-7447
PURE UUID: 78c6e6fc-613d-46c7-8f78-a355bd32e288
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Date deposited: 31 Jan 2017 15:29
Last modified: 16 Mar 2024 04:03
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Author:
Gabriele Boschetto
Author:
Hong-Tao Xue
Author:
Michal Krompiec
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