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

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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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References

  • 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 110:25462–25471

    CAS  PubMed  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • Baxter JB, Schmuttenmaer CA (2006) Conductivity of ZnO nanowires, nanoparticles, and thin films using time-resolved terahertz spectroscopy. J Phys Chem B 110:25229–25239

    CAS  PubMed  Google Scholar 

  • Carnio BN, Ahvazi B, Elezzabi AY (2016) Terahertz properties of cellulose nanocrystals and films. J Infrared Millim Terahertz Waves 37:281–288

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • Cooke DG, Krebs FC, Jepsen PU (2012) Direct observation of sub-100 fs mobile charge generation in a polymer-fullerene film. Phys Rev Lett 108:056603

    CAS  PubMed  Google Scholar 

  • 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

    Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • Dufresne A (2013) Nanocellulose: a new ageless bionanomaterial. Mat Today 16:220–227

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    Google Scholar 

  • Ferguson B, Zhang X-C (2002) Materials for terahertz science and technology. Nat Mater 1:26–33

    CAS  PubMed  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • Huang J, Zhu H, Chen Y, Preston C, Rohrbach K, Cumings J, Hu L (2013) Highly transparent and flexible nanopaper transistors. ACS Nano 7:2106–2113

    CAS  PubMed  Google Scholar 

  • Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cellulose nanofibers. Nanoscale 3:71–85

    CAS  PubMed  Google Scholar 

  • 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

    Google Scholar 

  • 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 6:7170

    PubMed  PubMed Central  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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 9:612

    CAS  PubMed Central  Google Scholar 

  • 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 14:1160–1165

    CAS  PubMed  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40:3941–3994

    CAS  PubMed  Google Scholar 

  • Nogi M, Karakawa M, Komoda N, Yagyu H, Nge TT (2015) Transparent conductive nanofiber paper for foldable solar cells. Sci Rep 5:17254

    CAS  PubMed  PubMed Central  Google Scholar 

  • 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

    CAS  Google Scholar 

  • Shi Z, Phillips GO, Yang G (2013) Nanocellulose electroconductive composites. Nanoscale 5:3194–3201

    CAS  PubMed  Google Scholar 

  • Smith NV (2001) Classical generalization of the Drude formula for the optical conductivity. Phys Rev B 64:155106

    Google Scholar 

  • Tonouchi M (2007) Cutting-edge terahertz technology. Nat Photonics 1:97–105

    CAS  Google Scholar 

  • Turner GM, Beard MC, Schmuttenmaer CA (2002) Carrier localization and cooling in dye-sensitized nanocrystalline titanium dioxide. J Phys Chem B 106:11716–11719

    CAS  Google Scholar 

  • 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

    Google Scholar 

  • Unuma T, Umemoto A, Kishida H (2013a) Anisotropic terahertz complex conductivities in oriented polythiophene films. Appl Phys Lett 103:213305

    Google Scholar 

  • 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

    Google Scholar 

  • 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

    Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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 10:386

    PubMed  PubMed Central  Google Scholar 

  • 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

    Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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 3:1536

    PubMed  PubMed Central  Google Scholar 

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Acknowledgments

T.U., O.K., and S.K. thank Prof. Kunihiko Tanaka at Nagaoka University of Technology for letting them use the UV/Vis/NIR spectrophotometer in his laboratory. This work was partly supported by JSPS KAKENHI Grant Number JP19K21966. J.J.S. acknowledges the Faculty of Science and Forestry at the University of Eastern Finland for the financial support (Grant No. 579/2017), and the Academy of Finland Photonics Research and Innovation (PREIN) Flagship Programme (Grant No. 320 166).

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Correspondence to Takeya Unuma.

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Unuma, T., Kobayashi, O., Kotaka, S. et al. Terahertz complex conductivity of cellulose nanocrystal based composite films controlled with PEDOT:PSS blending ratio. Cellulose 27, 10019–10027 (2020). https://doi.org/10.1007/s10570-020-03464-4

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