Block junction-functionalized all-conjugated donor-acceptor block copolymers.
File(s)Junction funct BCP Nübling_revised.docx (2.78 MB)
Accepted version
Author(s)
Type
Journal Article
Abstract
Junction-functionalized donor-acceptor (D-A) block copolymers (BCPs) enable spatial and electronic control over interfacial charge dynamics in excitonic devices such as solar cells. Here we present the design, synthesis, morphology and electronic characterization of block junction-functionalized, all-conjugated, all-crystalline D-A BCPs. Poly(3-hexylthiophene) (P3HT), a single thienylated diketopyrrolopyrrole (ThxDPPThx, x=1 or 2) unit and poly{[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (PNDIT2) is used as donor, interfacial unit and acceptor, respectively. Almost all C-C coupling steps are accomplished by virtue of C-H activation. Synthesis of the macroreagent H-P3HT-ThxDPPThx, with x determining its C-H reactivity, is key to the synthesis of various BCPs of type H-P3HT-ThxDPPThx-block-PNDIT2. Morphology is determined from a combination of calorimetry, transmission electron microscopy (TEM) and thin film scattering. Block copolymer crystallinity of P3HT and PNDIT2 is reduced indicating frustrated crystallization. A long period lp, is invisible from TEM, but shows up in resonant soft X-ray scattering experiments at a length scale of lp~ 60 nm. Photoluminescence of H-P3HT-ThxDPPThx indicates efficient transfer of the excitation energy to the DPP chain end, but is quenched in BCP films. Transient absorption and pump-push-photocurrent spectroscopies reveal geminate recombination (GR) as the main loss channel in as-prepared BCP films independent of junction functionalization. Melt-annealing increases GR as a result of the low degree of crystallinity and poorly defined interfaces, and additionally changes backbone orientation of PNDIT2 from face-on to edge-on. These morphological effects dominate solar cell performance and cause an insensitivity to the presence of the block junction.
Date Issued
2019-01-09
Date Acceptance
2018-12-07
Citation
ACS Applied Materials and Interfaces, 2019, 11 (1), pp.1143-1155
ISSN
1944-8244
Publisher
American Chemical Society
Start Page
1143
End Page
1155
Journal / Book Title
ACS Applied Materials and Interfaces
Volume
11
Issue
1
Copyright Statement
© 2018 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Applied Materials & Interfaces, after peer review and technical editing by the publisher. To access the final edited and published work see https://dx.doi.org/10.1021/acsami.8b18608
Sponsor
The Royal Society
Identifier
https://www.ncbi.nlm.nih.gov/pubmed/30523687
Grant Number
UF130178
Subjects
Science & Technology
Technology
Nanoscience & Nanotechnology
Materials Science, Multidisciplinary
Science & Technology - Other Topics
Materials Science
interfacial electron cascade
P3HT
PNDIT2
donor-acceptor block copolymers
all-conjugated block copolymer
transient absorption spectroscopy
HIGH-PERFORMANCE
DIRECT ARYLATION
GEMINATE RECOMBINATION
TRIBLOCK COPOLYMERS
PHASE-SEPARATION
MORPHOLOGY
POLYMERS
ENERGY
POLY(3-HEXYLTHIOPHENE)
CRYSTALLIZATION
0904 Chemical Engineering
0303 Macromolecular And Materials Chemistry
0306 Physical Chemistry (Incl. Structural)
Publication Status
Published
Coverage Spatial
United States
Date Publish Online
2018-12-07