Uncovering the Electronic State Interplay at Metal Oxide Electron Transport Layer/Nonfullerene Acceptor Interfaces in Stable Organic Photovoltaic Devices
(2023) In ACS Applied Materials and Interfaces 15(47). p.55065-55072- Abstract
The implementation of sputter-deposited TiOx as an electron transport layer in nonfullerene acceptor-based organic photovoltaics has been shown to significantly increase the long-term stability of devices compared to conventional solution-processed ZnO due to a decreased photocatalytic activity of the sputtered TiOx. In this work, we utilize synchrotron-based photoemission and absorption spectroscopies to investigate the interface between the electron transport layer, TiOx prepared by magnetron sputtering, and the nonfullerene acceptor, ITIC, prepared in situ by spray deposition to study the electronic state interplay and defect states at this interface. This is used to unveil the mechanisms behind the... (More)
The implementation of sputter-deposited TiOx as an electron transport layer in nonfullerene acceptor-based organic photovoltaics has been shown to significantly increase the long-term stability of devices compared to conventional solution-processed ZnO due to a decreased photocatalytic activity of the sputtered TiOx. In this work, we utilize synchrotron-based photoemission and absorption spectroscopies to investigate the interface between the electron transport layer, TiOx prepared by magnetron sputtering, and the nonfullerene acceptor, ITIC, prepared in situ by spray deposition to study the electronic state interplay and defect states at this interface. This is used to unveil the mechanisms behind the decreased photocatalytic activity of the sputter-deposited TiOx and thus also the increased stability of the organic solar cell devices. The results have been compared to similar measurements on anatase TiOx since anatase TiOx is known to have a strong photocatalytic activity. We show that the deposition of ITIC on top of the sputter-deposited TiOx results in an oxidation of Ti3+ species in the TiOx and leads to the emergence of a new O 1s peak that can be attributed to the oxygen in ITIC. In addition, increasing the thickness of ITIC on TiOx leads to a shift in the O 1s and C 1s core levels toward higher binding energies, which is consistent with electron transfer at the interface. Resonant photoemission at the Ti L-edge shows that oxygen vacancies in sputtered TiOx lie mostly in the surface region, which contrasts the anatase TiOx where an equal distribution between surface and subsurface oxygen vacancies is observed. Furthermore, it is shown that the subsurface oxygen vacancies in sputtered TiOx are strongly reduced after ITIC deposition, which can reduce the photocatalytic activity of the oxide, while the oxygen vacancies in model anatase TiOx are not affected upon ITIC deposition. This difference can explain the inferior photocatalytic activity of the sputter-deposited TiOx and thus also the increased stability of devices with sputter-deposited TiOx used as an electron transport layer.
(Less)
- author
- Ahmad, Mariam LU ; Cruguel, Hervé ; Ahmadpour, Mehrad ; Vannucchi, Noemi ; Samie, Nahed Mohammad ; Leuillet, Céline ; Generalov, Alexander LU ; Li, Zheshen ; Madsen, Morten and Witkowski, Nadine
- organization
- publishing date
- 2023-11-29
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- energy level alignment, metal oxide interfaces, nonfullerene acceptors, organic photovoltaics, photoemission
- in
- ACS Applied Materials and Interfaces
- volume
- 15
- issue
- 47
- pages
- 8 pages
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- pmid:37972316
- scopus:85178496561
- ISSN
- 1944-8244
- DOI
- 10.1021/acsami.3c11103
- language
- English
- LU publication?
- yes
- id
- b7a0b1d4-df17-4066-9ce4-636a1210969b
- date added to LUP
- 2024-01-04 12:27:26
- date last changed
- 2024-06-14 13:56:11
@article{b7a0b1d4-df17-4066-9ce4-636a1210969b,
abstract = {{<p>The implementation of sputter-deposited TiO<sub>x</sub> as an electron transport layer in nonfullerene acceptor-based organic photovoltaics has been shown to significantly increase the long-term stability of devices compared to conventional solution-processed ZnO due to a decreased photocatalytic activity of the sputtered TiO<sub>x</sub>. In this work, we utilize synchrotron-based photoemission and absorption spectroscopies to investigate the interface between the electron transport layer, TiO<sub>x</sub> prepared by magnetron sputtering, and the nonfullerene acceptor, ITIC, prepared in situ by spray deposition to study the electronic state interplay and defect states at this interface. This is used to unveil the mechanisms behind the decreased photocatalytic activity of the sputter-deposited TiO<sub>x</sub> and thus also the increased stability of the organic solar cell devices. The results have been compared to similar measurements on anatase TiO<sub>x</sub> since anatase TiO<sub>x</sub> is known to have a strong photocatalytic activity. We show that the deposition of ITIC on top of the sputter-deposited TiO<sub>x</sub> results in an oxidation of Ti<sup>3+</sup> species in the TiO<sub>x</sub> and leads to the emergence of a new O 1s peak that can be attributed to the oxygen in ITIC. In addition, increasing the thickness of ITIC on TiO<sub>x</sub> leads to a shift in the O 1s and C 1s core levels toward higher binding energies, which is consistent with electron transfer at the interface. Resonant photoemission at the Ti L-edge shows that oxygen vacancies in sputtered TiO<sub>x</sub> lie mostly in the surface region, which contrasts the anatase TiO<sub>x</sub> where an equal distribution between surface and subsurface oxygen vacancies is observed. Furthermore, it is shown that the subsurface oxygen vacancies in sputtered TiO<sub>x</sub> are strongly reduced after ITIC deposition, which can reduce the photocatalytic activity of the oxide, while the oxygen vacancies in model anatase TiO<sub>x</sub> are not affected upon ITIC deposition. This difference can explain the inferior photocatalytic activity of the sputter-deposited TiO<sub>x</sub> and thus also the increased stability of devices with sputter-deposited TiO<sub>x</sub> used as an electron transport layer.</p>}},
author = {{Ahmad, Mariam and Cruguel, Hervé and Ahmadpour, Mehrad and Vannucchi, Noemi and Samie, Nahed Mohammad and Leuillet, Céline and Generalov, Alexander and Li, Zheshen and Madsen, Morten and Witkowski, Nadine}},
issn = {{1944-8244}},
keywords = {{energy level alignment; metal oxide interfaces; nonfullerene acceptors; organic photovoltaics; photoemission}},
language = {{eng}},
month = {{11}},
number = {{47}},
pages = {{55065--55072}},
publisher = {{The American Chemical Society (ACS)}},
series = {{ACS Applied Materials and Interfaces}},
title = {{Uncovering the Electronic State Interplay at Metal Oxide Electron Transport Layer/Nonfullerene Acceptor Interfaces in Stable Organic Photovoltaic Devices}},
url = {{http://dx.doi.org/10.1021/acsami.3c11103}},
doi = {{10.1021/acsami.3c11103}},
volume = {{15}},
year = {{2023}},
}