Tuning of nonlinear optical bistability tuned by fullerene concentration in polyaniline-fullerene (PANI-C60) hybrid organic films

Third-order nonlinear optical (NLO) parameters, NLO absorption coefficient (β), imaginary part of susceptibility (χi(3)), saturation intensity and figure of merit of polyaniline–fullerene (PANI-C60) films were investigated using open-aperture z-scan measurement with a 532 nm Nd:YAG laser. Switching...

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Main Authors: Roshan Joseph Mathew, Syam Kishor K.S., Arun R. Chandran, Saji K.J., Sajeev U.S.
Format: Article
Language:English
Published: Elsevier 2025-01-01
Series:Next Nanotechnology
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Online Access:http://www.sciencedirect.com/science/article/pii/S2949829525001056
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author Roshan Joseph Mathew
Syam Kishor K.S.
Arun R. Chandran
Saji K.J.
Sajeev U.S.
author_facet Roshan Joseph Mathew
Syam Kishor K.S.
Arun R. Chandran
Saji K.J.
Sajeev U.S.
author_sort Roshan Joseph Mathew
collection DOAJ
description Third-order nonlinear optical (NLO) parameters, NLO absorption coefficient (β), imaginary part of susceptibility (χi(3)), saturation intensity and figure of merit of polyaniline–fullerene (PANI-C60) films were investigated using open-aperture z-scan measurement with a 532 nm Nd:YAG laser. Switching of saturable absorption (SA) to reverse saturable absorption (RSA) behaviour (NLO bistability) was observed in these organic hybrid films by changing the concentration of C60 in the PANI matrix. It is attributed to the charge transfer complex (CTC) formation between PANI and C60 in the film. PANI and low C₆₀-doped films exhibited SA, indicative of ground-state bleaching, while higher C₆₀ loadings triggered a switch to RSA due to enhanced excited-state absorption facilitated by efficient intersystem crossing induced by CTC formation. A transition from SA to RSA was confirmed from the observed sign reversal in β and χi(3). Values of β and χi(3), were shifted from –59.80 cm/GW to 99.3 cm/GW and –0.52 × 10−10 esu to 0.96 × 10−10 esu, respectively, in PANI and PANI-C₆₀. Films were prepared via the drop-casting technique with varying C₆₀ concentrations. SEM analysis showed morphological changes from uniform domains of PANI to C60-rich agglomerates. The CTC formation is confirmed by the FTIR and UV–visible absorption spectroscopy. The bandgap reduction from 2.62 eV in the PANI film to 2.20 eV at the highest C₆₀ concentration, with an increase in Urbach energy from 0.40 eV to 0.95 eV, indicated enhanced disorder and localised states. To the best of our knowledge, this is the first report of a concentration-driven SA-to-RSA transition in PANI–C₆₀ solid films, establishing their potential in photonic applications.
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spelling doaj-art-48d3de16875e4b98895caee7b562a96e2025-08-20T03:59:35ZengElsevierNext Nanotechnology2949-82952025-01-01810023610.1016/j.nxnano.2025.100236Tuning of nonlinear optical bistability tuned by fullerene concentration in polyaniline-fullerene (PANI-C60) hybrid organic filmsRoshan Joseph Mathew0Syam Kishor K.S.1Arun R. Chandran2Saji K.J.3Sajeev U.S.4Post Graduate and Research Department of Physics, Government College Kottayam, Kottayam, Kerala 686013, IndiaPost Graduate and Research Department of Physics, Government College Kottayam, Kottayam, Kerala 686013, India; Department of Physics, Government College Ambalapuzha, Alappuzha, Kerala 688561, IndiaInternational School of Photonics, Cochin University of Science and Technology, Cochin, Kerala 682022, IndiaInternational School of Photonics, Cochin University of Science and Technology, Cochin, Kerala 682022, IndiaPost Graduate and Research Department of Physics, Government College Kottayam, Kottayam, Kerala 686013, India; Department of Physics, Rajiv Gandhi Institute of Technology, Kottayam, Kerala 686501, India; Corresponding author at: Post Graduate and Research Department of Physics, Government College Kottayam, Kottayam, Kerala 686013, India.Third-order nonlinear optical (NLO) parameters, NLO absorption coefficient (β), imaginary part of susceptibility (χi(3)), saturation intensity and figure of merit of polyaniline–fullerene (PANI-C60) films were investigated using open-aperture z-scan measurement with a 532 nm Nd:YAG laser. Switching of saturable absorption (SA) to reverse saturable absorption (RSA) behaviour (NLO bistability) was observed in these organic hybrid films by changing the concentration of C60 in the PANI matrix. It is attributed to the charge transfer complex (CTC) formation between PANI and C60 in the film. PANI and low C₆₀-doped films exhibited SA, indicative of ground-state bleaching, while higher C₆₀ loadings triggered a switch to RSA due to enhanced excited-state absorption facilitated by efficient intersystem crossing induced by CTC formation. A transition from SA to RSA was confirmed from the observed sign reversal in β and χi(3). Values of β and χi(3), were shifted from –59.80 cm/GW to 99.3 cm/GW and –0.52 × 10−10 esu to 0.96 × 10−10 esu, respectively, in PANI and PANI-C₆₀. Films were prepared via the drop-casting technique with varying C₆₀ concentrations. SEM analysis showed morphological changes from uniform domains of PANI to C60-rich agglomerates. The CTC formation is confirmed by the FTIR and UV–visible absorption spectroscopy. The bandgap reduction from 2.62 eV in the PANI film to 2.20 eV at the highest C₆₀ concentration, with an increase in Urbach energy from 0.40 eV to 0.95 eV, indicated enhanced disorder and localised states. To the best of our knowledge, this is the first report of a concentration-driven SA-to-RSA transition in PANI–C₆₀ solid films, establishing their potential in photonic applications.http://www.sciencedirect.com/science/article/pii/S2949829525001056PANIFullereneCharge transfer complexRSAOptical limiting mechanism
spellingShingle Roshan Joseph Mathew
Syam Kishor K.S.
Arun R. Chandran
Saji K.J.
Sajeev U.S.
Tuning of nonlinear optical bistability tuned by fullerene concentration in polyaniline-fullerene (PANI-C60) hybrid organic films
Next Nanotechnology
PANI
Fullerene
Charge transfer complex
RSA
Optical limiting mechanism
title Tuning of nonlinear optical bistability tuned by fullerene concentration in polyaniline-fullerene (PANI-C60) hybrid organic films
title_full Tuning of nonlinear optical bistability tuned by fullerene concentration in polyaniline-fullerene (PANI-C60) hybrid organic films
title_fullStr Tuning of nonlinear optical bistability tuned by fullerene concentration in polyaniline-fullerene (PANI-C60) hybrid organic films
title_full_unstemmed Tuning of nonlinear optical bistability tuned by fullerene concentration in polyaniline-fullerene (PANI-C60) hybrid organic films
title_short Tuning of nonlinear optical bistability tuned by fullerene concentration in polyaniline-fullerene (PANI-C60) hybrid organic films
title_sort tuning of nonlinear optical bistability tuned by fullerene concentration in polyaniline fullerene pani c60 hybrid organic films
topic PANI
Fullerene
Charge transfer complex
RSA
Optical limiting mechanism
url http://www.sciencedirect.com/science/article/pii/S2949829525001056
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