General bis(fluorophenyl azide) photo-crosslinkers for conjugated and non-conjugated polyelectrolytes

Teo, Desmond W. Y.; Jamal, Zaini; Seah, Qiu-Jing; Png, Rui‐Qi; Chua, Lay‐Lay

doi:10.1039/c9tc04060a

Cited by 10 publications

(17 citation statements)

References 27 publications

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“…sFPA82-TfO was synthesized following Teo et al . The TfO form tends to be more soluble than the halide form.…”

Section: Resultsmentioning

confidence: 99%

“…General. sFPA82-TfO was synthesized following Teo et al 25 The TfO form tends to be more soluble than the halide form. The extension of conjugation by the bis(methylene)-1,1dimethyl-4-piperidonium bridging unit downshifts the primary π−π* absorption A-and B-bands.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Here, we demonstrate that, contrary to expectations, ζ ≈ 1 for an ionic crosslinker in a hole-doped π-conjugated polymer matrix, which has an ultrahigh work function (WF) of 5.75 eV, without requiring rigorous dehydration, and without degrading the work function and hole-injection properties of the crosslinked film. The ionic crosslinker tested is 3,5-bis(4-azido-3,5-difluoro-2,6-diisopropylbenzylidene)-1,1-dimethyl-4-oxopiperidin-1-ium trifluoromethanesulfonate (sFPA82-TfO; chemical structures in Figure a), an example of a sterically substituted ionic bisFPA we have developed recently with the absorption band edge that extends to the i-line (365 nm) . The polymer tested is the self-compensated, hole-doped polymer, poly(9,9-bis(3-(pentafluoroethanesulfonylimidosulfonyl)propyl)fluorene-2,7-diyl- alt -1,4-phenylene-( m -trifluoromethylphenylimino)-1,4-phenylene) (mTFF-C 2 F 5 SIS-Na), an important model of solution-processable hole-injection polymers .…”

Section: Introductionmentioning

confidence: 99%

“…The ionic crosslinker tested is 3,5-bis(4azido-3,5-difluoro-2,6-diisopropylbenzylidene)-1,1-dimethyl-4oxopiperidin-1-ium trifluoromethanesulfonate (sFPA82-TfO; chemical structures in Figure 1a), an example of a sterically substituted ionic bisFPA we have developed recently with the absorption band edge that extends to the i-line (365 nm). 25 The polymer tested is the self-compensated, hole-doped p o l y m e r , p o l y ( 9 , 9 -b i s ( 3 -(pentafluoroethanesulfonylimidosulfonyl)propyl)fluorene-2,7diyl-alt-1,4-phenylene-(m-trifluoromethylphenylimino)-1,4phenylene) (mTFF-C 2 F 5 SIS-Na), an important model of solution-processable hole-injection polymers. 26 Crosslinking of the mTFF-C 2 F 5 SIS-Na layer leads to lower diode leakage and better solar cell characteristics in diagnostic devices.…”

Section: ■ Introductionmentioning

confidence: 99%

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Nearly 100% Photocrosslinking Efficiency in Ultrahigh Work Function Hole-Doped Conjugated Polymers Using Bis(fluorophenyl azide) Additives

Teo

Jamal

Phua

et al. 2019

ACS Appl. Mater. Interfaces

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Self-compensated (SC) hole-doped conjugated polyelectrolytes with high work functions can provide efficient hole-injection and -collection layers for organic and other semiconductor devices. If these films can be photocrosslinked, the semiconductor overlayer can be deposited from a wider range of solvents, enabling flexibility in device design and fabrication. However, a generic photocrosslinking methodology for these materials is not yet available. Here, we demonstrate that sFPA82-TfO, the recently developed bis(fluorophenyl azide) photocrosslinker that is also i-line compatible, can surprisingly give 100% efficient photocrosslinking for SC hole-doped conjugated polyelectrolytes, i.e., one crosslink per reactive moiety, using mTFF-C2F5SIS-Na, a triarylamine–fluorene copolymer, as the model polyelectrolyte, without degrading its ultrahigh work function of 5.75 eV. The photocrosslinking efficiency is much higher than in the corresponding undoped polyelectrolyte and nonconjugated polyelectrolyte films, where the efficiency is only 20%. We attribute this improvement to the formation of smaller ion multiplet clusters in the hole-doped polyelectrolyte, as suggested by molecular dynamics simulations and infrared spectroscopy, which prevents occlusion of the ionic crosslinker. Photocrosslinking of the SC hole-doped mTFF-C2F5SIS-Na film used as a hole-injection layer in 100 nm-thick PFOP diodes suppresses the leakage current by over 3 orders of magnitude compared to those without crosslinking, to below 30 nA cm–2 at ±2 V. Photocrosslinking of the same film used as the hole-collection layer in PBDTTPD:PC61BM solar cells produces a higher photocurrent density, fill factor, and power conversion efficiency.

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“…sFPA82-TfO was synthesized following Teo et al . The TfO form tends to be more soluble than the halide form.…”

Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Nearly 100% Photocrosslinking Efficiency in Ultrahigh Work Function Hole-Doped Conjugated Polymers Using Bis(fluorophenyl azide) Additives

Teo

Jamal

Phua

et al. 2019

ACS Appl. Mater. Interfaces

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“…Photochemical generation of reactive intermediates such as radicals, − nitrenes, − cations, − bases, , and protons − is a method for initiating useful chemical reactions that require high spatiotemporal specificity. The specificity from photochemical processes enables applications in numerous areas including photopharmacology, photoimaging, and photolithography.…”

Section: Introductionmentioning

confidence: 99%

Photoacid Generators Activated through Sequential Two-Photon Excitation: 1-Sulfonatoxy-2-alkoxyanthraquinone Derivatives

2021

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Two sulfonate ester derivatives of anthraquinone, 1-tosyloxy-2-methoxy-9,10-anthraquinone (1a) and 1-trifluoromethylsulfonoxy-2-methoxy-9,10-anthraquinone (1b) were prepared and their ability to produce strong acids upon photoexcitation was examined. It is shown that these compounds generate acid with a yield that increases with light intensity when the applied photon dose is held constant. Additional experiments show that the rate of acid generation increases 4 fold when visible light (532 nm) laser pulses are combined with ultraviolet (355 nm) compared with ultraviolet alone.Continuous wave diode laser photolysis also effects acid generation with a rate that depends quadratically on the light intensity. Density functional theory calculations, laser flash photolysis, and chemical trapping experiments support a mechanism whereby an initially formed triplet state (T 1 ) is excited to a higher triplet state which in turn undergoes homolysis of the RS(O 2 )-OAr bond. Secondary reactions of the initially formed sulfonyl radicals produce strong acids. It is demonstrated that high intensity photolysis of either 1a or 1b can initiate cationic polymerization of ethyl vinyl ether.

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Research progress on crosslinked polymer-based dielectrics for thin film capacitors

Wang,

Lu,

Meng

et al. 2024

Polym. Bull.

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General bis(fluorophenyl azide) photo-crosslinkers for conjugated and non-conjugated polyelectrolytes

Abstract: Photo-patterning and crosslinking of polymer semiconductors, charge injection and/or transport layers are essential to improve the performance and/or functionality of organic semiconductor devices.

Cited by 10 publications

References 27 publications

Nearly 100% Photocrosslinking Efficiency in Ultrahigh Work Function Hole-Doped Conjugated Polymers Using Bis(fluorophenyl azide) Additives

Nearly 100% Photocrosslinking Efficiency in Ultrahigh Work Function Hole-Doped Conjugated Polymers Using Bis(fluorophenyl azide) Additives

Photoacid Generators Activated through Sequential Two-Photon Excitation: 1-Sulfonatoxy-2-alkoxyanthraquinone Derivatives

Research progress on crosslinked polymer-based dielectrics for thin film capacitors

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