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Blazinic, V., Ericsson, L., Levine, I., Hansson, R., Opitz, A. & Moons, E. (2019). Impact of intentional photo-oxidation of a donor polymer and PC70BM on solar cell performance. Physical Chemistry, Chemical Physics - PCCP, 21, 22259-22271
Open this publication in new window or tab >>Impact of intentional photo-oxidation of a donor polymer and PC70BM on solar cell performance
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2019 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 21, p. 22259-22271Article in journal (Refereed) Published
Abstract [en]

A short lifetime is the main factor hindering the wider implementation of low-cost organic photovoltaics in large-area and outdoor applications. Ingress of oxygen and water vapour through non-ideal encapsulation layers is a known cause of degradation for polymer/fullerene based solar cells. To better understand the origin of this performance degradation, we study the effect of intentional exposure of the photo-active layer to simulated sunlight (AM1.5) in air both on the solar cell performance and on the molecular semiconductor materials. Cathode-free thin films of a blend of the electron donor polymer poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl] (TQ1) and the electron acceptor fullerene derivative [6,6]-phenyl-C70-butyric acid methyl ester (PC70BM) were exposed to simulated sunlight in air. Fourier-transform infrared spectra demonstrate the formation of carbonyl photo-oxidation products in the blend films, as well as in the pristine polymer and fullerene films. Solar cells prepared with photo-oxidized active layers show increasingly degraded electrical performance (lower short circuit current, open circuit voltage and fill factor) with increasing exposure time. The increased diode ideality factor indicates that trap-assisted recombination hinders device operation after exposure. The external quantum efficiency decreases drastically with increasing exposure time over the whole photon energy range, while the UV-vis absorption spectra of the blend films only show a mild photo-induced bleaching. This demonstrates that not only the photo-induced degradation of the solar cell performance is not predominantly caused by the loss in light absorption, but charge transport and collection are also hampered. This is explained by the fact that photo-oxidation of PC70BM causes bonds in its conjugated cage to break, as evidenced by the decreased ∏* intensity in C1s-NEXAFS spectra of PC70BM films. This degradation of unoccupied states of PC70BM will hinder the transport of photo-generated electrons to the electrode. Surface photovoltage spectroscopy gives direct evidence for gap states at the surface of a PC70BM film, formed after 2 hours of exposure and resulting in upward band bending at the PC70BM/air surface. These observations indicate that the photo-oxidation of PC70BM is likely to be the main cause of the performance degradation observed when the photoactive layer of a TQ1:PC70BM solar cell is intentionally exposed to light in air.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2019
National Category
Physical Sciences
Research subject
Physics
Identifiers
urn:nbn:se:kau:diva-75110 (URN)10.1039/C9CP04384E (DOI)000491079900005 ()
Funder
Swedish Energy Agency, 38327-1
Available from: 2019-10-07 Created: 2019-10-07 Last updated: 2019-11-14Bibliographically approved
Blazinic, V. (2019). Probing the effects of photodegradation of acceptor materials in polymer solar cells: bulk, surface, and molecular level. (Doctoral dissertation). Karlstads universitet
Open this publication in new window or tab >>Probing the effects of photodegradation of acceptor materials in polymer solar cells: bulk, surface, and molecular level
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Polymer solar cells (PSC) have reached record power conversion efficiencies of over 15%. The operational lifetime of PSCs, however, has to increase for their use in large area outdoor applications. In this work, a set of spectroscopic techniques (UV-vis, FTIR, NEXAFS, XPS) was used to study the impact of exposure to light and air (photo-oxidation) on the photoactive layer and its components. We focused on the electron acceptor components: the fullerene derivatives, PC60BM and PC70BM, and the polymer N2200. A comparative study of photo-oxidized PC60BM and PC70BM thin films by UV-vis and FTIR spectroscopy has shown that both materials undergo similar photochemical transformation, with the process being faster in PC60BM, due to the greater curvature of the C60 cage. Comparing experimental FTIR, XPS and NEXAFS spectra of the photo-oxidized PC60BM thin films with the calculated spectra for a large variety of photo-oxidation products, it was found that dicarbonyl and anhydride groups attach to the C60 cage during photo-oxidation. The study of photo-oxidized TQ1:PC70BM blend films by spectroscopic and J-V measurements shows that deterioration of the charge transport in PC70BM is the major contributor to the device performance degradation. Kelvin Probe measurements demonstrated that the charge transport deterioration was due to upward band bending and gap states being formed on the surface of photo-oxidized PC70BM. The TQ1:PC70BM blends films were further studied by AFM-IR in order to determine the lateral distribution of pristine components, as well as the photo-oxidation products. It was found that anhydride oxidation products of PC70BM are equally distributed over the blend film surface. The PC70BM is replaced with the polymer N2200 in the blend with TQ1. The photostability in air of the blend and its neat components was studied by UV-vis and FTIR spectroscopy. The spectra show that thermal annealing improves the photostability in air of both components.

Abstract [en]

Increase of the global energy demand and the climate change are two factors motivating the study and use of renewable energy sources, such as the solar energy. Organic photovoltaics (OPV) is a technology that uses organic molecules to convert solar energy into electricity. These organic molecules can be kept in ink form, allowing OPV device manufacture via coating, and ultimately roll-to-roll printing techniques, resulting in inexpensive, light weight, portable, and mechanically flexible sources of electricity. OPV devices have reached over 15% in power conversion efficiency, but their operational lifetime has to increase.

In this work, the photostability of the active layer in organic solar cells and its molecular components was studied by a variety of spectroscopy, microscopy and electrical characterization techniques, with focus on the chemical changes that these materials undergo during exposure to light and air. The aim was to determine the relation between materials’ degradation and the device performance degradation.

Place, publisher, year, edition, pages
Karlstads universitet, 2019. p. 59
Series
Karlstad University Studies, ISSN 1403-8099 ; 2019:30
Keywords
photovoltaics, polymer solar cell, conjugated polymers, fullerene, photo-oxidation, spectroscopy
National Category
Physical Sciences
Research subject
Physics
Identifiers
urn:nbn:se:kau:diva-75093 (URN)978-91-7867-054-3 (ISBN)978-91-7867-064-2 (ISBN)
Public defence
2019-11-29, 21A 342 Eva Erikssonsalen, 13:15 (English)
Opponent
Supervisors
Available from: 2019-11-05 Created: 2019-10-08 Last updated: 2020-01-28Bibliographically approved
Blazinic, V., Ericsson, L., Muntean, S. A. & Moons, E. (2018). Photo-degradation in air of spin-coated PC60BM and PC70BM films. Synthetic metals, 241, 26-30
Open this publication in new window or tab >>Photo-degradation in air of spin-coated PC60BM and PC70BM films
2018 (English)In: Synthetic metals, ISSN 0379-6779, E-ISSN 1879-3290, Vol. 241, p. 26-30Article in journal (Refereed) Published
Abstract [en]

The fullerene derivatives PC60BM and PC70BM are widely used as electron accepting components in the active layer of polymer solar cells. Here we compare their photochemical stability by exposing thin films of PC60BM and PC70BM to simulated sunlight in ambient air for up to 47 h, and study changes in their UV–vis and FT-IR spectra. We quantify the photo-degradation by tracking the development of oxidation products in the transmission FT-IR spectra. Results indicate that PC60BM photodegrades faster than PC70BM. The rate of photo-oxidation of the thin films is dependent on the rate of oxygen diffusion in to the film and on the photo-oxidation rate of a single molecule. Both factors are dependent on the nature of the fullerene cage. The faster photo-oxidation of PC60BM than of PC70BM is in agreement with its slightly lower density and its higher reactivity. The use of PC70BM in solar cells is advantageous not only because of its absorption spectrum, but also because of its higher stability.

Place, publisher, year, edition, pages
Elsevier, 2018
Keywords
Fullerene derivatives, Photo-oxidation, UV-vis spectroscopy, IR spectroscopy
National Category
Condensed Matter Physics
Research subject
Materials Science
Identifiers
urn:nbn:se:kau:diva-66953 (URN)10.1016/j.synthmet.2018.03.021 (DOI)000432504000004 ()
Available from: 2018-04-09 Created: 2018-04-09 Last updated: 2019-11-08Bibliographically approved
Hansson, R., Ericsson, L., Holmes, N. P., Blazinic, V., Dastoor, P. & Moons, E. (2017). Opportunities and challenges in probing local composition of organic material blends for photovoltaics. Journal of Materials Research, 32(10), 1982-1992
Open this publication in new window or tab >>Opportunities and challenges in probing local composition of organic material blends for photovoltaics
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2017 (English)In: Journal of Materials Research, ISSN 0884-2914, E-ISSN 2044-5326, Vol. 32, no 10, p. 1982-1992Article in journal (Refereed) Published
Place, publisher, year, edition, pages
Materials Research Society, 2017
National Category
Physical Sciences
Identifiers
urn:nbn:se:kau:diva-47259 (URN)10.1557/jmr.2017.7 (DOI)000402284600014 ()
Funder
Swedish Energy Agency, 38327-1Swedish Research Council, 2015-03778Göran Gustafsson Foundation for Research in Natural Sciences and Medicine
Available from: 2016-11-23 Created: 2016-11-23 Last updated: 2019-11-21Bibliographically approved
Ericsson, L., Blazinic, V. & Moons, E.Effects of the morphology on the photodegradation of TQ1:PC70BM film: an AFM-IR study.
Open this publication in new window or tab >>Effects of the morphology on the photodegradation of TQ1:PC70BM film: an AFM-IR study
(English)Manuscript (preprint) (Other academic)
Keywords
photoactive layer, photo-oxidation, fullerene, conjugated polymer, AFM-IR
National Category
Physical Sciences
Research subject
Materials Science
Identifiers
urn:nbn:se:kau:diva-75122 (URN)
Note

Manuscript

Available from: 2019-10-07 Created: 2019-10-07 Last updated: 2019-11-05
Blazinic, V., Ericsson, L. & Moons, E.Stability of TQ1:N2200 active layers for all-polymer solar cells.
Open this publication in new window or tab >>Stability of TQ1:N2200 active layers for all-polymer solar cells
(English)Manuscript (preprint) (Other academic)
Keywords
polymer solar cell, polymer donor, polymer acceptor, non-fullerene acceptor, photo-oxidation, UV-vis, FT-IR
National Category
Physical Sciences
Research subject
Materials Science
Identifiers
urn:nbn:se:kau:diva-75124 (URN)
Note

Manuscript

Available from: 2019-10-07 Created: 2019-10-07 Last updated: 2019-10-08
Brumboiu, I. E., Ericsson, L., Blazinic, V., Hansson, R., Opitz, A., Brena, B. & Moons, E.The Photooxidation of PC60BM: New Insights from Spectroscopy.
Open this publication in new window or tab >>The Photooxidation of PC60BM: New Insights from Spectroscopy
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

In the quest towards more durable solution-processed solar cells, the stability of the active layer materials under operation conditions is important. While lifetimes of several years have been demonstrated for encapsulated organic solar cells, it is generally known that degradation events can be accounted for by air components (O2 and/or water vapour) leaking into the cell through a non-ideal sealing. Here we present a fundamental study of intentional photo-degradation of the electron-acceptor PC60BM ([6,6]-phenyl-C61-butyric acid methyl ester) in air, with the purpose of improving the understanding of the electronic effects of fullerene photo-oxidation. We have studied spincoated thin films of PC60BM by X-ray Photoelectron Spectroscopy, Near-edge X-ray Absorption Fine Structure spectroscopy, and Fourier Transform Infrared Spectroscopy, before and after exposing them to simulated sunlight in air. The changes observed in the spectra obtained by these complementary methods were compared with calculated spectra of a large set of possible oxidation products of PC60BM where oxygen atoms have been attached to the C60 cage. The best fit with experimental IR spectra of photodegraded PC60BM films was obtained for a linear combination of calculated spectra for two degradation products, a dicarbonyl and an anhydride, both with open cages with 58 carbon atoms, and the pristine PC60BM molecule. From this comparison, we conclude that the conjugation of the fullerene cage is disturbed by the formation of several carbonyl-based derivatives on the C60 cage, accompanied by a transition from sp2 to sp3-hybridized carbon. The π* resonance in the C1s NEXAFS spectrum was found to be a very sensitive probe for small changes to the fullerene cage, and FT-IR was needed in combination with O1s NEXAFS, to identify the oxidation products.

Keywords
photodegradation, fullerene, density functional theory, NEXAFS, XPS, FTIR
National Category
Physical Sciences
Identifiers
urn:nbn:se:kau:diva-75121 (URN)
Note

Manuscript

Available from: 2019-10-07 Created: 2019-10-07 Last updated: 2019-10-08
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0002-7533-4860

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