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Plasma induced degradation and surface electronic structure modification of Poly(3-hexylthiophene) films

Plasma induced degradation and surface electronic structure modification of Poly(3-hexylthiophene) films
Plasma induced degradation and surface electronic structure modification of Poly(3-hexylthiophene) films

Plasma treatment is an environmentally friendly solution for modifying or nanostructuring the surface of several materials including photoactive polymers. The detailed characterization of the effect of plasma treatment on chemical and optoelectronic properties of photoactive polymers is, therefore, of specific interest. Herein, the effect of the exposure of poly(3-hexylthiophene) (P3HT) thin films to plasma created in three different gases (oxygen, argon and hydrogen) was studied. A range of spectroscopic techniques, such as x-ray (XPS) and ultraviolet (UPS) photoelectron spectroscopy in conjunction with UV–vis absorption, Fourier transform infrared (FTIR) and photoluminescence (PL) spectroscopies, are employed to quantify the extent of chemical modification occurring in each particular case. It is shown that oxygen plasma treatment leads to the disruption of the π-conjugation via the direct oxidation of the sulfur atom of the thiophene ring while the aliphatic side chain remains nearly unaffected. An oxidation mechanism is proposed according to which the sulfur atom of the thiophene ring is oxidized into sulfoxides and sulfones, which subsequently degraded into sulfonates or sulfonic acids in a relatively small degree. For argon and hydrogen plasma treatments some oxidation products are detected only at the polymer surface. In all cases the polymer surface Fermi level is shifted closer to the highest occupied molecular orbital (HOMO) energy after plasma treatment indicating p-type doping arising from surface oxidation.

Argon, Hydrogen, Oxygen, P3HT, Plasma, Surface electronic structure, Thiophene oxidation
0141-3910
162-172
Tountas, Marinos
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Georgiadou, Dimitra G.
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Zeniou, Angelos
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Seintis, Kostas
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Soultati, Anastasia
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Polydorou, Ermioni
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Gardelis, Spyros
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Douvas, Antonios M.
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Speliotis, Thanassis
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Tsikritzis, Dimitris
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Kennou, Stella
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Fakis, Mihalis
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Gogolides, Evangelos
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Tsoukalas, Dimitris
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Argitis, Panagiotis
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Vasilopoulou, Maria
aad1381e-d091-4090-8c7c-b74bed22393d
Tountas, Marinos
6c5da1dc-9396-4570-866a-f72923cb94ae
Georgiadou, Dimitra G.
84977176-3678-4fb3-a3dd-2044a49c853b
Zeniou, Angelos
c51352e0-de9e-47b1-8916-9ad3a8c1c65c
Seintis, Kostas
528905de-49bf-41af-85aa-b4074b8c9968
Soultati, Anastasia
75205fde-50fc-473e-ad72-ab0b3c6b2cb9
Polydorou, Ermioni
98bfe710-9802-432e-83fa-63c4afd5bd05
Gardelis, Spyros
e1c19249-ca1b-44c3-bb48-3cf76362f388
Douvas, Antonios M.
2e088659-e1b3-4723-aff9-4dfe385579b5
Speliotis, Thanassis
986b7ee1-eee5-4f27-a6ab-dc0099e343c2
Tsikritzis, Dimitris
f86716a6-2f5f-49b2-bc9b-945217515bc6
Kennou, Stella
7ca6a6bd-6a05-4110-b3da-c8807f798370
Fakis, Mihalis
ed01170e-ba9c-48d8-87d3-02a05ad0eff0
Gogolides, Evangelos
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Tsoukalas, Dimitris
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Argitis, Panagiotis
ab9c4ea6-3dd2-4e34-935d-81bfb360f358
Vasilopoulou, Maria
aad1381e-d091-4090-8c7c-b74bed22393d

Tountas, Marinos, Georgiadou, Dimitra G., Zeniou, Angelos, Seintis, Kostas, Soultati, Anastasia, Polydorou, Ermioni, Gardelis, Spyros, Douvas, Antonios M., Speliotis, Thanassis, Tsikritzis, Dimitris, Kennou, Stella, Fakis, Mihalis, Gogolides, Evangelos, Tsoukalas, Dimitris, Argitis, Panagiotis and Vasilopoulou, Maria (2018) Plasma induced degradation and surface electronic structure modification of Poly(3-hexylthiophene) films. Polymer Degradation and Stability, 149, 162-172. (doi:10.1016/j.polymdegradstab.2017.12.010).

Record type: Article

Abstract

Plasma treatment is an environmentally friendly solution for modifying or nanostructuring the surface of several materials including photoactive polymers. The detailed characterization of the effect of plasma treatment on chemical and optoelectronic properties of photoactive polymers is, therefore, of specific interest. Herein, the effect of the exposure of poly(3-hexylthiophene) (P3HT) thin films to plasma created in three different gases (oxygen, argon and hydrogen) was studied. A range of spectroscopic techniques, such as x-ray (XPS) and ultraviolet (UPS) photoelectron spectroscopy in conjunction with UV–vis absorption, Fourier transform infrared (FTIR) and photoluminescence (PL) spectroscopies, are employed to quantify the extent of chemical modification occurring in each particular case. It is shown that oxygen plasma treatment leads to the disruption of the π-conjugation via the direct oxidation of the sulfur atom of the thiophene ring while the aliphatic side chain remains nearly unaffected. An oxidation mechanism is proposed according to which the sulfur atom of the thiophene ring is oxidized into sulfoxides and sulfones, which subsequently degraded into sulfonates or sulfonic acids in a relatively small degree. For argon and hydrogen plasma treatments some oxidation products are detected only at the polymer surface. In all cases the polymer surface Fermi level is shifted closer to the highest occupied molecular orbital (HOMO) energy after plasma treatment indicating p-type doping arising from surface oxidation.

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More information

Accepted/In Press date: 12 December 2017
e-pub ahead of print date: 14 December 2017
Published date: 1 March 2018
Keywords: Argon, Hydrogen, Oxygen, P3HT, Plasma, Surface electronic structure, Thiophene oxidation

Identifiers

Local EPrints ID: 440621
URI: http://eprints.soton.ac.uk/id/eprint/440621
ISSN: 0141-3910
PURE UUID: 21581e9e-03cc-4642-89c9-426cb695053e
ORCID for Dimitra G. Georgiadou: ORCID iD orcid.org/0000-0002-2620-3346

Catalogue record

Date deposited: 12 May 2020 16:46
Last modified: 07 Oct 2020 02:27

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Contributors

Author: Marinos Tountas
Author: Angelos Zeniou
Author: Kostas Seintis
Author: Anastasia Soultati
Author: Ermioni Polydorou
Author: Spyros Gardelis
Author: Antonios M. Douvas
Author: Thanassis Speliotis
Author: Dimitris Tsikritzis
Author: Stella Kennou
Author: Mihalis Fakis
Author: Evangelos Gogolides
Author: Dimitris Tsoukalas
Author: Panagiotis Argitis
Author: Maria Vasilopoulou

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