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Published in: Cellulose 17/2020

23-09-2020 | Original Research

Terahertz complex conductivity of cellulose nanocrystal based composite films controlled with PEDOT:PSS blending ratio

Authors: Takeya Unuma, Omou Kobayashi, Shoya Kotaka, Rajesh Koppolu, Martti Toivakka, Jarkko J. Saarinen

Published in: Cellulose | Issue 17/2020

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Abstract

We investigate the terahertz complex conductivity spectra of cellulose nanocrystal (CNC) based composite films fabricated with different blending ratios of the conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) and without/with glycerol additive. A partially localized nature of carriers in the composite is clearly seen in the obtained spectral shapes of complex conductivity and is well described by an extended Drude model. We find that the carriers become denser and less localized with increasing PEDOT:PSS blending ratio and that the addition of glycerol to the composite is efficacious in enhancing carrier delocalization as well as mechanical flexibility.

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Literature
go back to reference Ai X, Beard MC, Knutsen KP, Shaheen SE, Rumbles G, Ellingson RJ (2006) Photoinduced charge carrier generation in a poly(3-hexylthiophene) and methanofullerene bulk heterojunction investigated by time-resolved terahertz spectroscopy. J Phys Chem B 110:25462–25471PubMed Ai X, Beard MC, Knutsen KP, Shaheen SE, Rumbles G, Ellingson RJ (2006) Photoinduced charge carrier generation in a poly(3-hexylthiophene) and methanofullerene bulk heterojunction investigated by time-resolved terahertz spectroscopy. J Phys Chem B 110:25462–25471PubMed
go back to reference Alam KM, Kar P, Thakur UK, Kisslinger R, Mahdi N, Mohammadpour A, Baheti PA, Kumar P, Shankar K (2019) Remarkable self-organization and unusual conductivity behavior in cellulose nanocrystal-PEDOT: PSS nanocomposites. J Mater Sci: Mater Electron 30:1390–1399 Alam KM, Kar P, Thakur UK, Kisslinger R, Mahdi N, Mohammadpour A, Baheti PA, Kumar P, Shankar K (2019) Remarkable self-organization and unusual conductivity behavior in cellulose nanocrystal-PEDOT: PSS nanocomposites. J Mater Sci: Mater Electron 30:1390–1399
go back to reference Andrianov AV, Aleshin AN, Khripunov AK, Trukhin VN (2015) Terahertz properties of bacterial cellulose films and its composite with conducting polymer PEDOT/PSS. Synth Metals 205:201–205 Andrianov AV, Aleshin AN, Khripunov AK, Trukhin VN (2015) Terahertz properties of bacterial cellulose films and its composite with conducting polymer PEDOT/PSS. Synth Metals 205:201–205
go back to reference Baxter JB, Schmuttenmaer CA (2006) Conductivity of ZnO nanowires, nanoparticles, and thin films using time-resolved terahertz spectroscopy. J Phys Chem B 110:25229–25239PubMed Baxter JB, Schmuttenmaer CA (2006) Conductivity of ZnO nanowires, nanoparticles, and thin films using time-resolved terahertz spectroscopy. J Phys Chem B 110:25229–25239PubMed
go back to reference Carnio BN, Ahvazi B, Elezzabi AY (2016) Terahertz properties of cellulose nanocrystals and films. J Infrared Millim Terahertz Waves 37:281–288 Carnio BN, Ahvazi B, Elezzabi AY (2016) Terahertz properties of cellulose nanocrystals and films. J Infrared Millim Terahertz Waves 37:281–288
go back to reference Cielecka I, Szustak M, Kalinowska H, Gendaszewska-Darmach E, Ryngajłło M, Maniukiewicz W, Bielecki S (2019) Glycerol-plasticized bacterial nanocellulose-based composites with enhanced flexibility and liquid sorption capacity. Cellulose 26:5409–5426 Cielecka I, Szustak M, Kalinowska H, Gendaszewska-Darmach E, Ryngajłło M, Maniukiewicz W, Bielecki S (2019) Glycerol-plasticized bacterial nanocellulose-based composites with enhanced flexibility and liquid sorption capacity. Cellulose 26:5409–5426
go back to reference Cooke DG, Krebs FC, Jepsen PU (2012) Direct observation of sub-100 fs mobile charge generation in a polymer-fullerene film. Phys Rev Lett 108:056603PubMed Cooke DG, Krebs FC, Jepsen PU (2012) Direct observation of sub-100 fs mobile charge generation in a polymer-fullerene film. Phys Rev Lett 108:056603PubMed
go back to reference Cooke DG, MacDonald AN, Hryciw A, Wang J, Li Q, Meldrum A, Hegmann FA (2006) Transient terahertz conductivity in photoexcited silicon nanocrystal films. Phys Rev B 73:193311 Cooke DG, MacDonald AN, Hryciw A, Wang J, Li Q, Meldrum A, Hegmann FA (2006) Transient terahertz conductivity in photoexcited silicon nanocrystal films. Phys Rev B 73:193311
go back to reference Crispin X, Marciniak S, Osikowicz W, Zotti G, van der Gon AWD, Louwet F, Fahlman M, Groenendaal L, de Schryver F, Salaneck WR (2003) Conductivity, morphology, interfacial chemistry, and stability of poly(3,4ethylene dioxythiophene)-poly(styrene sulfonate): A photoelectron spectroscopy study. J Polym Sci, Part B 41:2561 Crispin X, Marciniak S, Osikowicz W, Zotti G, van der Gon AWD, Louwet F, Fahlman M, Groenendaal L, de Schryver F, Salaneck WR (2003) Conductivity, morphology, interfacial chemistry, and stability of poly(3,4ethylene dioxythiophene)-poly(styrene sulfonate): A photoelectron spectroscopy study. J Polym Sci, Part B 41:2561
go back to reference Cunningham PD, Hayden LM (2008) Carrier dynamics resulting from above and below gap excitation of P3HT and P3HT/PCBM investigated by optical-pump terahertz-probe spectroscopy. J Phys Chem C 112:7928–7935 Cunningham PD, Hayden LM (2008) Carrier dynamics resulting from above and below gap excitation of P3HT and P3HT/PCBM investigated by optical-pump terahertz-probe spectroscopy. J Phys Chem C 112:7928–7935
go back to reference Darpentigny C, Molina-Boisseau S, Nonglaton G, Bras J, Jean B (2020) Ice-templated freeze-dried cryogels from tunicate cellulose nanocrystals with high specific surface area and anisotropic morphological and mechanical properties. Cellulose 27:233–247 Darpentigny C, Molina-Boisseau S, Nonglaton G, Bras J, Jean B (2020) Ice-templated freeze-dried cryogels from tunicate cellulose nanocrystals with high specific surface area and anisotropic morphological and mechanical properties. Cellulose 27:233–247
go back to reference Dufresne A (2013) Nanocellulose: a new ageless bionanomaterial. Mat Today 16:220–227 Dufresne A (2013) Nanocellulose: a new ageless bionanomaterial. Mat Today 16:220–227
go back to reference Eichhorn SJ, Dufresne A, Aranguren M, Marcovich NE, Capadona JR, Rowan SJ, Weder C, Thielemans W, Roman M, Renneckar S, Gindl W, Veigel S, Keckes J, Yano H, Abe K, Nogi M, Nakagaito AN, Mangalam A, Simonsen J, Benight AS, Bismarck A, Berglund LA, Peijs T (2010) Review: current international research into cellulose nanofibres and nanocomposites. J Mater Sci 45:1–33 Eichhorn SJ, Dufresne A, Aranguren M, Marcovich NE, Capadona JR, Rowan SJ, Weder C, Thielemans W, Roman M, Renneckar S, Gindl W, Veigel S, Keckes J, Yano H, Abe K, Nogi M, Nakagaito AN, Mangalam A, Simonsen J, Benight AS, Bismarck A, Berglund LA, Peijs T (2010) Review: current international research into cellulose nanofibres and nanocomposites. J Mater Sci 45:1–33
go back to reference Elfwing A, Ponseca CS Jr, Ouyang L, Urbanowicz A, Krotkus A, Tu D, Forchheimer R, Inganäs O (2018) Conducting helical structures from celery decorated with a metallic conjugated polymer give resonances in the terahertz range. Adv Funct Mater 28:1706595 Elfwing A, Ponseca CS Jr, Ouyang L, Urbanowicz A, Krotkus A, Tu D, Forchheimer R, Inganäs O (2018) Conducting helical structures from celery decorated with a metallic conjugated polymer give resonances in the terahertz range. Adv Funct Mater 28:1706595
go back to reference Ferguson B, Zhang X-C (2002) Materials for terahertz science and technology. Nat Mater 1:26–33PubMed Ferguson B, Zhang X-C (2002) Materials for terahertz science and technology. Nat Mater 1:26–33PubMed
go back to reference Fujisaki Y, Koga H, Nakajima Y, Nakata M, Tsuji H, Yamamoto T, Kurita T, Nogi M, Shimidzu N (2014) Transparent nanopaper-based flexible organic thin-film transistor array. Adv Funct Mater 24:1657–1663 Fujisaki Y, Koga H, Nakajima Y, Nakata M, Tsuji H, Yamamoto T, Kurita T, Nogi M, Shimidzu N (2014) Transparent nanopaper-based flexible organic thin-film transistor array. Adv Funct Mater 24:1657–1663
go back to reference Greczynski G, Kugler T, Keil M, Osikowicz W, Fahlman M, Salaneck WR (2001) Photoelectron spectroscopy of thin films of PEDOT-PSS conjugated polymer blend: a mini-review and some new results. J Electron Spectrosc Relat Phenom 121:1 Greczynski G, Kugler T, Keil M, Osikowicz W, Fahlman M, Salaneck WR (2001) Photoelectron spectroscopy of thin films of PEDOT-PSS conjugated polymer blend: a mini-review and some new results. J Electron Spectrosc Relat Phenom 121:1
go back to reference Hu L, Zheng G, Yao J, Liu N, Weil B, Eskilsson M, Karabulut E, Ruan Z, Fan S, Bloking JT, McGehee MD, Wagberg L, Cui Y (2013) Transparent and conductive paper from nanocellulose fibers. Energy Environ Sci 6:513–518 Hu L, Zheng G, Yao J, Liu N, Weil B, Eskilsson M, Karabulut E, Ruan Z, Fan S, Bloking JT, McGehee MD, Wagberg L, Cui Y (2013) Transparent and conductive paper from nanocellulose fibers. Energy Environ Sci 6:513–518
go back to reference Huang J, Zhu H, Chen Y, Preston C, Rohrbach K, Cumings J, Hu L (2013) Highly transparent and flexible nanopaper transistors. ACS Nano 7:2106–2113PubMed Huang J, Zhu H, Chen Y, Preston C, Rohrbach K, Cumings J, Hu L (2013) Highly transparent and flexible nanopaper transistors. ACS Nano 7:2106–2113PubMed
go back to reference Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cellulose nanofibers. Nanoscale 3:71–85PubMed Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cellulose nanofibers. Nanoscale 3:71–85PubMed
go back to reference Jönsson SKM, Birgerson J, Crispin X, Greczynski G, Osikowicz W, van der Gon AWD, Salaneck WR, Fahlman M (2003) The effects of solvents on the morphology and sheet resistance in poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT-PSS) films. Synth Met 139:1 Jönsson SKM, Birgerson J, Crispin X, Greczynski G, Osikowicz W, van der Gon AWD, Salaneck WR, Fahlman M (2003) The effects of solvents on the morphology and sheet resistance in poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT-PSS) films. Synth Met 139:1
go back to reference Jung YH, Chang T-H, Zhang H, Yao C, Zheng Q, Yang VW, Mi H, Kim M, Cho SJ, Park D-W, Jiang H, Lee J, Qiu Y, Zhou W, Cai Z, Gong S, Ma Z (2015) High-performance green flexible electronics based on biodegradable cellulose nanofibril paper. Nat Commun 6:7170PubMedPubMedCentral Jung YH, Chang T-H, Zhang H, Yao C, Zheng Q, Yang VW, Mi H, Kim M, Cho SJ, Park D-W, Jiang H, Lee J, Qiu Y, Zhou W, Cai Z, Gong S, Ma Z (2015) High-performance green flexible electronics based on biodegradable cellulose nanofibril paper. Nat Commun 6:7170PubMedPubMedCentral
go back to reference Klemm D, Kramer F, Moritz S, Lindström T, Ankerfors M, Gray D, Dorris A (2011) Nanocelluloses: a new family of nature-based materials. Angew Chem Int Ed 50:5438–5466 Klemm D, Kramer F, Moritz S, Lindström T, Ankerfors M, Gray D, Dorris A (2011) Nanocelluloses: a new family of nature-based materials. Angew Chem Int Ed 50:5438–5466
go back to reference Ko Y, Kim J, Kim D, Kwon G, Yamauchi Y, You J (2019) Fabrication of highly conductive porous cellulose/PEDOT:PSS nanocomposite paper via post-treatment. Nanomaterials 9:612PubMedCentral Ko Y, Kim J, Kim D, Kwon G, Yamauchi Y, You J (2019) Fabrication of highly conductive porous cellulose/PEDOT:PSS nanocomposite paper via post-treatment. Nanomaterials 9:612PubMedCentral
go back to reference Koga H, Saito T, Kitaoka T, Nogi M, Suganuma K, Isogai A (2013) Transparent, conductive, and printable composites consisting of TEMPO-oxidized nanocellulose and carbon nanotube. Biomacromolecules 14:1160–1165PubMed Koga H, Saito T, Kitaoka T, Nogi M, Suganuma K, Isogai A (2013) Transparent, conductive, and printable composites consisting of TEMPO-oxidized nanocellulose and carbon nanotube. Biomacromolecules 14:1160–1165PubMed
go back to reference Lee K, Menon R, Yoon CO, Heeger AJ (1995) Reflectance of conducting polypyrrole: observation of the metal-insulator transition driven by disorder. Phys Rev B 52:4779–4787 Lee K, Menon R, Yoon CO, Heeger AJ (1995) Reflectance of conducting polypyrrole: observation of the metal-insulator transition driven by disorder. Phys Rev B 52:4779–4787
go back to reference Lloyd-Hughes J, Jeon T-I (2012) A review of the terahertz conductivity of bulk and nano-materials. J Infrared Millim Terahertz Waves 33:871–925 Lloyd-Hughes J, Jeon T-I (2012) A review of the terahertz conductivity of bulk and nano-materials. J Infrared Millim Terahertz Waves 33:871–925
go back to reference Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40:3941–3994PubMed Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40:3941–3994PubMed
go back to reference Nogi M, Karakawa M, Komoda N, Yagyu H, Nge TT (2015) Transparent conductive nanofiber paper for foldable solar cells. Sci Rep 5:17254PubMedPubMedCentral Nogi M, Karakawa M, Komoda N, Yagyu H, Nge TT (2015) Transparent conductive nanofiber paper for foldable solar cells. Sci Rep 5:17254PubMedPubMedCentral
go back to reference Palumbiny CM, Heller C, Schaffer CJ, Körstgens V, Santoro G, Roth SV (2014) Molecular reorientation and structural changes in cosolvent treated highly conductive PEDOT:PSS electrodes for flexible indium tin oxide-free organic electronics. J Phys Chem C 118:13598–13606 Palumbiny CM, Heller C, Schaffer CJ, Körstgens V, Santoro G, Roth SV (2014) Molecular reorientation and structural changes in cosolvent treated highly conductive PEDOT:PSS electrodes for flexible indium tin oxide-free organic electronics. J Phys Chem C 118:13598–13606
go back to reference Shi Z, Phillips GO, Yang G (2013) Nanocellulose electroconductive composites. Nanoscale 5:3194–3201PubMed Shi Z, Phillips GO, Yang G (2013) Nanocellulose electroconductive composites. Nanoscale 5:3194–3201PubMed
go back to reference Smith NV (2001) Classical generalization of the Drude formula for the optical conductivity. Phys Rev B 64:155106 Smith NV (2001) Classical generalization of the Drude formula for the optical conductivity. Phys Rev B 64:155106
go back to reference Tonouchi M (2007) Cutting-edge terahertz technology. Nat Photonics 1:97–105 Tonouchi M (2007) Cutting-edge terahertz technology. Nat Photonics 1:97–105
go back to reference Turner GM, Beard MC, Schmuttenmaer CA (2002) Carrier localization and cooling in dye-sensitized nanocrystalline titanium dioxide. J Phys Chem B 106:11716–11719 Turner GM, Beard MC, Schmuttenmaer CA (2002) Carrier localization and cooling in dye-sensitized nanocrystalline titanium dioxide. J Phys Chem B 106:11716–11719
go back to reference Unuma T, Fujii K, Kishida H, Nakamura A (2010) Terahertz complex conductivities of carriers with partial localization in doped polythiophenes. Appl Phys Lett 97:033308 Unuma T, Fujii K, Kishida H, Nakamura A (2010) Terahertz complex conductivities of carriers with partial localization in doped polythiophenes. Appl Phys Lett 97:033308
go back to reference Unuma T, Umemoto A, Kishida H (2013a) Anisotropic terahertz complex conductivities in oriented polythiophene films. Appl Phys Lett 103:213305 Unuma T, Umemoto A, Kishida H (2013a) Anisotropic terahertz complex conductivities in oriented polythiophene films. Appl Phys Lett 103:213305
go back to reference Unuma T, Yamada N, Nakamura A, Kishida H, Lee S-C, Hong E-Y, Lee S-H, Kwon O-P (2013b) Direct observation of carrier delocalization in highly conducting polyaniline. Appl Phys Lett 103:053303 Unuma T, Yamada N, Nakamura A, Kishida H, Lee S-C, Hong E-Y, Lee S-H, Kwon O-P (2013b) Direct observation of carrier delocalization in highly conducting polyaniline. Appl Phys Lett 103:053303
go back to reference Unuma T, Yoshikawa M, Nakamura A, Kishida H (2016) Segmentation of conducting domains in PEDOT:PSS films induced by an additive for conductivity enhancement. Appl Phys Express 9:051601 Unuma T, Yoshikawa M, Nakamura A, Kishida H (2016) Segmentation of conducting domains in PEDOT:PSS films induced by an additive for conductivity enhancement. Appl Phys Express 9:051601
go back to reference Unuma T, Kobayashi O, Hamdany IFA, Kumar V, Saarinen JJ (2019) Terahertz complex conductivity of nanofibrillar cellulose-PEDOT:PSS composite films. Cellulose 26:3247–3253 Unuma T, Kobayashi O, Hamdany IFA, Kumar V, Saarinen JJ (2019) Terahertz complex conductivity of nanofibrillar cellulose-PEDOT:PSS composite films. Cellulose 26:3247–3253
go back to reference Valtakari D, Liu J, Kumar V, Xu C, Toivakka M, Saarinen JJ (2015) Conductivity of PEDOT:PSS on spin-coated and drop cast nanofibrillar cellulose thin films. Nanoscale Res Lett 10:386PubMedPubMedCentral Valtakari D, Liu J, Kumar V, Xu C, Toivakka M, Saarinen JJ (2015) Conductivity of PEDOT:PSS on spin-coated and drop cast nanofibrillar cellulose thin films. Nanoscale Res Lett 10:386PubMedPubMedCentral
go back to reference Walther M, Cooke DG, Sherstan C, Hajar M, Freeman MR, Hegmann FA (2007) Terahertz conductivity of thin gold films at the metal-insulator percolation transition. Phys Rev B 76:125408 Walther M, Cooke DG, Sherstan C, Hajar M, Freeman MR, Hegmann FA (2007) Terahertz conductivity of thin gold films at the metal-insulator percolation transition. Phys Rev B 76:125408
go back to reference Xie WQ, Yu KX, Gong YX (2019) Preparation of fluorescent and antibacterial nanocomposite films based on cellulose nanocrystals/ZnS quantum dots/polyvinyl alcohol. Cellulose 26:2363–2373 Xie WQ, Yu KX, Gong YX (2019) Preparation of fluorescent and antibacterial nanocomposite films based on cellulose nanocrystals/ZnS quantum dots/polyvinyl alcohol. Cellulose 26:2363–2373
go back to reference Zhou Y, Fuentes-Hernandez C, Khan TM, Liu J-C, Hsu J, Shim JW, Dindar A, Youngblood JP, Moon RJ, Kippelen B (2013) Recyclable organic solar cells on cellulose nanocrystal substrates. Sci Rep 3:1536PubMedPubMedCentral Zhou Y, Fuentes-Hernandez C, Khan TM, Liu J-C, Hsu J, Shim JW, Dindar A, Youngblood JP, Moon RJ, Kippelen B (2013) Recyclable organic solar cells on cellulose nanocrystal substrates. Sci Rep 3:1536PubMedPubMedCentral
Metadata
Title
Terahertz complex conductivity of cellulose nanocrystal based composite films controlled with PEDOT:PSS blending ratio
Authors
Takeya Unuma
Omou Kobayashi
Shoya Kotaka
Rajesh Koppolu
Martti Toivakka
Jarkko J. Saarinen
Publication date
23-09-2020
Publisher
Springer Netherlands
Published in
Cellulose / Issue 17/2020
Print ISSN: 0969-0239
Electronic ISSN: 1572-882X
DOI
https://doi.org/10.1007/s10570-020-03464-4

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