Realizing Saturable Absorption and Reverse Saturable Absorption in a PEDOT:PSS Film via Electrical Modulation.

Electrical tuning of the nonlinear absorption of materials has promising application potential, while studies remain rare. In this work, we show that the third-order nonlinear absorption of poly(3,4-ethylenedioxythiophene) chemically doped with poly(styrene sulfonic acid) [PEDOT:PSS] can be effectively modulated by external voltage. The nonlinear absorption of the film can be varied between reverse saturable absorption (RSA) and saturable absorption (SA) via voltage control with laser excitation at 800 nm, and the corresponding nonlinear absorption coefficient can be tuned in the range -1606 ± 73 to 521 ± 9 cm GW-1. The doping level and energy structure of PEDOT are modulated with different voltages. The undoped film affords two-photon absorption and accordingly the RSA response. A moderately doped sample has two polaron levels, and Pauli blocking associated with these two polaron levels results in SA. The bipolaron level in heavily doped PEDOT leads to excited-state absorption and therefore RSA behavior. The approach reported here can be applied to other semiconductors and is a convenient, effective, and promising method for the electrical tuning of the optical nonlinearity.

[1]  Zuxing Zhang,et al.  Photochemically Derived Plasmonic Semiconductor Nanocrystals as an Optical Switch for Ultrafast Photonics , 2020 .

[2]  R. Demadrille,et al.  Progress in understanding structure and transport properties of PEDOT-based materials: A critical review , 2020 .

[3]  W. Cai,et al.  Electrically Biased Silicon Metasurfaces with Magnetic Mie Resonance for Tunable Harmonic Generation of Light , 2019, ACS Photonics.

[4]  K. Cheah,et al.  Gigantic electric-field-induced second harmonic generation from an organic conjugated polymer enhanced by a band-edge effect , 2019, Light, science & applications.

[5]  Fengqiu Wang,et al.  An Ultrabroadband Mid‐Infrared Pulsed Optical Switch Employing Solution‐Processed Bismuth Oxyselenide , 2018, Advanced materials.

[6]  R. Agarwal,et al.  Strong modulation of second-harmonic generation with very large contrast in semiconducting CdS via high-field domain , 2018, Nature Communications.

[7]  E. Reed,et al.  Structural phase transition in monolayer MoTe2 driven by electrostatic doping , 2017, Nature.

[8]  Giulio Cerullo,et al.  Broadband, electrically tunable third-harmonic generation in graphene , 2017, Nature Nanotechnology.

[9]  Young Sun,et al.  A Synaptic Transistor based on Quasi‐2D Molybdenum Oxide , 2017, Advanced materials.

[10]  Shian Zhang,et al.  A Solution‐Processed Ultrafast Optical Switch Based on a Nanostructured Epsilon‐Near‐Zero Medium , 2017, Advanced materials.

[11]  J. Wierzbowski,et al.  Electric-Field Switchable Second-Harmonic Generation in Bilayer MoS2 by Inversion Symmetry Breaking. , 2017, Nano letters.

[12]  G. Xie,et al.  Universal Near-Infrared and Mid-Infrared Optical Modulation for Ultrafast Pulse Generation Enabled by Colloidal Plasmonic Semiconductor Nanocrystals. , 2016, ACS nano.

[13]  W. Cai,et al.  Electrically Tunable Harmonic Generation of Light from Plasmonic Structures in Electrolytes. , 2016, Nano letters.

[14]  J. Coleman,et al.  Ultrafast Nonlinear Excitation Dynamics of Black Phosphorus Nanosheets from Visible to Mid-Infrared. , 2016, ACS nano.

[15]  Robert W. Boyd,et al.  Large optical nonlinearity of indium tin oxide in its epsilon-near-zero region , 2016, Science.

[16]  Zhiyong Xiao,et al.  Multimodal Nonlinear Optical Imaging of MoS₂ and MoS₂-Based van der Waals Heterostructures. , 2016, ACS nano.

[17]  Xianjie Liu,et al.  An Organic Mixed Ion–Electron Conductor for Power Electronics , 2015, Advanced science.

[18]  Duk-Yong Choi,et al.  Ultrafast All-Optical Switching with Magnetic Resonances in Nonlinear Dielectric Nanostructures. , 2015, Nano letters.

[19]  Aaron M. Jones,et al.  Electrical control of second-harmonic generation in a WSe2 monolayer transistor. , 2015, Nature nanotechnology.

[20]  Jun Wang,et al.  Giant two‐photon absorption in monolayer MoS2 , 2015, 1503.02259.

[21]  G. Duesberg,et al.  Direct Observation of Degenerate Two-Photon Absorption and Its Saturation in WS2 and MoS2 Monolayer and Few-Layer Films. , 2015, ACS nano.

[22]  J. Cox,et al.  Electrically tunable nonlinear plasmonics in graphene nanoislands , 2014, Nature Communications.

[23]  Yonghao Cui,et al.  Electrifying photonic metamaterials for tunable nonlinear optics , 2014, Nature Communications.

[24]  H. Kishida,et al.  Microscopic Mobility of Polarons in Chemically Doped Polythiophenes Measured by Employing Photoluminescence Spectroscopy , 2014 .

[25]  S. Chou,et al.  Enhancement and electric charge-assisted tuning of nonlinear light generation in bipolar plasmonics. , 2014, Nano letters.

[26]  J. Coleman,et al.  Ultrafast saturable absorption of two-dimensional MoS2 nanosheets. , 2013, ACS nano.

[27]  Kevin G. Gallagher,et al.  Correlating hysteresis and voltage fade in lithium- and manganese-rich layered transition-metal oxide electrodes , 2013 .

[28]  Alexander J. Cowan,et al.  Charge carrier trapping, recombination and transfer in hematite (α-Fe2O3) water splitting photoanodes , 2013 .

[29]  Alok P. Vasudev,et al.  Electrically Controlled Nonlinear Generation of Light with Plasmonics , 2011, Science.

[30]  X. Crispin,et al.  Optimization of the thermoelectric figure of merit in the conducting polymer poly(3,4-ethylenedioxythiophene). , 2011, Nature materials.

[31]  C. Rao,et al.  Femtosecond carrier dynamics and saturable absorption in graphene suspensions , 2009, 0911.1415.

[32]  H von Holst,et al.  Toxicity evaluation of PEDOT/biomolecular composites intended for neural communication electrodes , 2009, Biomedical materials.

[33]  Inge Asselberghs,et al.  Redox-switching of nonlinear optical behavior in Langmuir-Blodgett thin films containing a ruthenium(II) ammine complex. , 2008, Journal of the American Chemical Society.

[34]  Ion Cohanoschi,et al.  Z-scan theoretical analysis for three-, four- and five-photon absorption , 2007 .

[35]  J. Vittal,et al.  AgInSe2 nanorods: A semiconducting material for saturable absorber , 2007, 0710.5573.

[36]  K. Clays,et al.  Electrochemical, spectroelectrochemical, and molecular quadratic and cubic nonlinear optical properties of alkynylruthenium dendrimers. , 2006, Journal of the American Chemical Society.

[37]  Magnus Berggren,et al.  Electrochemical control of surface wettability of poly(3-alkylthiophenes) , 2006 .

[38]  Hendry. I. Elim,et al.  Observation of saturable and reverse-saturable absorption at longitudinal surface plasmon resonance in gold nanorods , 2006, cond-mat/0604651.

[39]  Mark G. Humphrey,et al.  Organometallic complexes for nonlinear optics. 33. Electrochemical switching of the third-order nonlinearity observed by simultaneous femtosecond degenerate four-wave mixing and pump-probe measurements , 2003 .

[40]  M. Samoć,et al.  Organometallic complexes for nonlinear optics. 30.1 electrochromic linear and nonlinear optical properties of alkynylbis(diphosphine)ruthenium complexes. , 2003, Journal of the American Chemical Society.

[41]  M. Samoć,et al.  Organometallic Complexes for Nonlinear Optics. 24. Reversible Electrochemical Switching of Nonlinear Absorption , 2001 .

[42]  Serge Lefrant,et al.  Raman Spectroscopic Studies of Regioregular Poly(3-alkylthiophenes) , 1996 .

[43]  B. Liedberg,et al.  In situ spectroscopic investigations of electrochromism and ion transport in a poly (3,4-ethylenedioxythiophene) electrode in a solid state electrochemical cell , 1994 .

[44]  Joel S. Miller,et al.  Molecular materials V Part B†. Molecular nonlinear optical materials–potential applications , 1991 .

[45]  E. W. Stryland,et al.  Sensitive Measurement of Optical Nonlinearities Using a Single Beam Special 30th Anniversary Feature , 1990 .

[46]  R. Zitter.  SATURATED OPTICAL ABSORPTION THROUGH BAND FILLING IN SEMICONDUCTORS , 1969 .

[47]  Q. Xiong,et al.  Phonon‐Assisted Anti‐Stokes Lasing in ZnTe Nanoribbons , 2016, Advanced materials.

[48]  Mark A. Ratner,et al.  Molecular and Macromolecular Nonlinear Optical Materials. Probing Architecture/Electronic Structure/Frequency Doubling Relationships via an SCF-LCAO MECI π Electron Formalism , 1988 .

[49]  Fred Wudl,et al.  Optical properties of conducting polymers , 1988 .

[50]  A. Heeger.  Charge Storage in Conducting Polymers: Solitons, Polarons, and Bipolarons , 1985 .