Please use this identifier to cite or link to this item: https://hdl.handle.net/20.500.14279/28910
Title: Doping-induced decomposition of organic semiconductors: a caveat to the use of Lewis acid p-dopants
Authors: Rotas, Georgios 
Antoniou, Giannis N. 
Papagiorgis, Paris 
Basu, Aniruddha 
Panidi, Julianna 
Ufimkin, Petr 
Tsetseris, Leonidas 
Itskos, Grigorios 
Heeney, Martin 
Vougioukalakis, Georgios C. 
Anthopoulos, Thomas D. 
Keivanidis, Panagiotis E. 
Major Field of Science: Engineering and Technology
Field Category: Materials Engineering
Keywords: Absorption spectroscopy;Density functional theory;Electronic properties;Electrospray ionization;Mass spectrometry;Nuclear magnetic resonance;Semiconductor doping;Substrates;Thin layer chromatography;Ultraviolet spectroscopy
Issue Date: 21-Sep-2022
Source: Journal of Materials Chemistry C, 2022, vol. 10, no. 35, pp. 12751-12764
Volume: 10
Issue: 35
Start page: 12751
End page: 12764
Journal: Journal of Materials Chemistry C 
Abstract: Solution-processable molecular dopants are popular wet-lab mediators to engineer the electronic properties of organic semiconductors and to optimize the level performance of their corresponding devices. Nonetheless, the exact doping mechanism that is operative during the interaction of organic semiconductors with Lewis acid species is not fully elaborated. The products of the doping reactions between Lewis acids and organic semiconductors have not been studied in detail. Here we focus on the macromolecular poly[bis(4-phenyl)(2,4-dimethylphenyl)]amine (PTAA) and molecular fluorinated anthradithiophene (diF-TES-ADT) organic semiconductors for addressing their chemical integrity after p-doping by the tris(pentafluorophenyl) borane [B(C6F5)3] Lewis acid agent. The PTAA and diF-TES-ADT organic substrates are studied in mixtures with B(C6F5)3 at three discrete concentration regimes. In the dilute solution regime, UV-Vis absorption spectroscopy verifies the effectiveness of p-doping by the changes observed in the absorption spectra of the solutions at increased B(C6F5)3 content. In the concentrated solution regime, the reactivity of B(C6F5)3 with PTAA and diF-TES-ADT is monitored by proton nuclear magnetic resonance (1H-NMR) and electrospray ionization mass spectroscopy (ES-MS), as well as thin-layer chromatography (TLC). Finally, in the solid-state the photophysical properties of spin-coated PTAA:B(C6F5)3 and diF-TES-ADT:B(C6F5)3 films are examined as a function of their B(C6F5)3 content. Density functional theory (DFT) calculations corroborate the experimental findings. Both theoretical and experimental results exclude the formation of Lewis adduct species in the PTAA:B(C6F5)3 and diF-TES-ADT:B(C6F5)3 systems. In agreement with recent literature, the B(C6F5)3 reactivity is attributed to the Brønsted-type acidity of the hydrated B(C6F5)3-OH2 complex that induces p-doping via the protonation of the organic substrates. The formation of the B(C6F5)3-OH2 acidic agent is identified experimentally by its characteristic 1H-NMR signal at 4.7 ppm. All results for the three concentration regimes provide evidence for the occurrence of PTAA and diF-TES-ADT decomposition in the presence of B(C6F5)3. At high B(C6F5)3 loadings, ES-MS spectroscopy and TLC analysis suggest that B(C6F5)3 remains unreacted, revealing the catalytic role in the decomposition process of PTAA and diF-TES-ADT. The results suggest that after interacting with Lewis acids, organic semiconductors may undergo detrimental decomposition reactions. This potentially undesired chemical reactivity should be considered for evaluating the operation stability of the p-doped electronic devices.
URI: https://hdl.handle.net/20.500.14279/28910
ISSN: 20507534
DOI: 10.1039/d2tc03048a
Rights: © Royal Society of Chemistry
Attribution-NonCommercial-NoDerivatives 4.0 International
Type: Article
Affiliation : University of Ioannina 
National and Kapodistrian University of Athens 
Cyprus University of Technology 
University of Cyprus 
King Abdullah University of Science and Technology 
Imperial College London 
Publication Type: Peer Reviewed
Appears in Collections:Άρθρα/Articles

CORE Recommender
Show full item record

SCOPUSTM   
Citations

3
checked on Mar 14, 2024

WEB OF SCIENCETM
Citations

3
Last Week
0
Last month
0
checked on Oct 29, 2023

Page view(s)

195
Last Week
4
Last month
1
checked on Dec 25, 2024

Google ScholarTM

Check

Altmetric


This item is licensed under a Creative Commons License Creative Commons