Spray coated high-conductivity PEDOT:PSS transparent electrodes for stretchable and mechanically-robust organic solar cells

Abstract High conductivity poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) was spray cast to form highly flexible transparent electrodes for forward- and inverted-mode organic solar cells (OSCs). A multiple solvent ink containing ethylene glycol was developed, and a post-deposition annealing step contributed to a high conductivity of 1070±50 S cm−1. Sheet resistance and transmission at a wavelength of 550 nm were controlled within 24–259 Ω □−1 and 71–95%, respectively, which are amongst the best-reported combined characteristics. Forward-mode OSCs with spray coated PEDOT:PSS anodes yielded a power conversion efficiency of 3.2%. Mechanical bending and stretching tests demonstrated that the flexibility of these PEDOT:PSS layers were far superior to that of ITO: elastic moduli were reduced by more than an order of magnitude, and the resistance increased far more slowly under both uniaxial stretching and bending to progressively smaller radii of curvature. With these experiments, the minimum radii of curvature and maximum uniaxial strains at which acceptable performance is maintained were investigated. Collectively, our results illustrate a promising future for the scalable printing of low-cost PEDOT:PSS-based flexible transparent electrodes.

[1]  Mikkel Jørgensen,et al.  Upscaling of polymer solar cell fabrication using full roll-to-roll processing. , 2010, Nanoscale.

[2]  F. Krebs Fabrication and processing of polymer solar cells: A review of printing and coating techniques , 2009 .

[3]  M. Hamasha,et al.  Behavior of Sputtered Indium–Tin–Oxide Thin Film on Poly-Ethylene Terephthalate Substrate Under Stretching , 2011, Journal of Display Technology.

[4]  R. Stoltenberg,et al.  Evaluation of solution-processed reduced graphene oxide films as transparent conductors. , 2008, ACS nano.

[5]  Yang Xu,et al.  Comparative study on different carbon nanotube materials in terms of transparent conductive coatings. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[6]  Jianyong Ouyang,et al.  PEDOT:PSS films with significantly enhanced conductivities induced by preferential solvation with cosolvents and their application in polymer photovoltaic cells , 2011 .

[7]  Tae-Wook Kim,et al.  Evolution of nanomorphology and anisotropic conductivity in solvent-modified PEDOT:PSS films for polymeric anodes of polymer solar cells , 2009 .

[8]  A. J. Heeger,et al.  Photoinduced Electron Transfer from a Conducting Polymer to Buckminsterfullerene , 1992, Science.

[9]  Zhenan Bao,et al.  Organic light-emitting diodes on solution-processed graphene transparent electrodes. , 2010, ACS nano.

[10]  Xiangang Luo,et al.  Efficiency Enhancement of Organic Solar Cells Using Transparent Plasmonic Ag Nanowire Electrodes , 2010, Advanced materials.

[11]  Bernard Kippelen,et al.  Optimization of a polymer top electrode for inverted semitransparent organic solar cells , 2011 .

[12]  Robert C. Tenent,et al.  Transparent conductive single-walled carbon nanotube networks with precisely tunable ratios of semiconducting and metallic nanotubes. , 2008, ACS nano.

[13]  John R. Reynolds,et al.  Transparent, Conductive Carbon Nanotube Films , 2004, Science.

[14]  Husnu Emrah Unalan,et al.  Conducting and transparent single-wall carbon nanotube electrodes for polymer-fullerene solar cells , 2005 .

[15]  Seok‐In Na,et al.  Efficient and Flexible ITO‐Free Organic Solar Cells Using Highly Conductive Polymer Anodes , 2008 .

[16]  C. J. M. Emmott,et al.  Environmental and economic assessment of ITO-free electrodes for organic solar cells , 2012 .

[17]  Thomas M. Higgins,et al.  Silver Nanowire Networks as Flexible, Transparent, Conducting Films: Extremely High DC to Optical Conductivity Ratios. , 2009, ACS nano.

[18]  G. Pharr,et al.  Nanoindentation of Soft Films on Hard Substrates:The Importance of Pile-Up , 1996 .

[19]  Wolfgang Mühleisen,et al.  Highly efficient organic solar cells with printable low-cost transparent contacts , 2008 .

[20]  M H Andrew Ng,et al.  Efficient coating of transparent and conductive carbon nanotube thin films on plastic substrates , 2008, Nanotechnology.

[21]  J. Dual,et al.  Mechanical characterization of PEDOT : PSS thin films , 2009 .

[22]  Yi Cui,et al.  Scalable coating and properties of transparent, flexible, silver nanowire electrodes. , 2010, ACS nano.

[23]  N. Camaioni,et al.  Polymer- and carbon-based electrodes for polymer solar cells: Toward low-cost, continuous fabrication over large area , 2012 .

[24]  A. Alsayed,et al.  Highly Conductive Poly(3,4‐ethylenedioxythiophene):Poly (styrenesulfonate) Films Using 1‐Ethyl‐3‐methylimidazolium Tetracyanoborate Ionic Liquid , 2012 .

[25]  Liangbing Hu,et al.  Organic solar cells with carbon nanotube network electrodes , 2006 .

[26]  Eun Hye Kim,et al.  The crystallinity and mechanical properties of indium tin oxide coatings on polymer substrates , 2011 .

[27]  K. Fehse,et al.  Highly Conductive Polymer Anodes as Replacements for Inorganic Materials in High‐Efficiency Organic Light‐Emitting Diodes , 2007 .

[28]  Xiaoling Fan,et al.  The electrical stabilities of flexible ITO thin films on buffer layer coated PET , 2008, 2008 Asia Optical Fiber Communication & Optoelectronic Exposition & Conference.

[29]  Yi Cui,et al.  Electrospun metal nanofiber webs as high-performance transparent electrode. , 2010, Nano letters.

[30]  Mikkel Jørgensen,et al.  ITO-free flexible polymer solar cells: From small model devices to roll-to-roll processed large modules , 2011 .

[31]  J. Hummelen,et al.  Polymer Photovoltaic Cells: Enhanced Efficiencies via a Network of Internal Donor-Acceptor Heterojunctions , 1995, Science.

[32]  Zhenan Bao,et al.  Highly Conductive and Transparent PEDOT:PSS Films with a Fluorosurfactant for Stretchable and Flexible Transparent Electrodes , 2012 .

[33]  Brian J. Worfolk,et al.  Finely tailored performance of inverted organic photovoltaics through layer-by-layer interfacial engineering. , 2011, ACS applied materials & interfaces.

[34]  Paul Heremans,et al.  Influence of cathode oxidation via the hole extraction layer in polymer:fullerene solar cells , 2011 .

[35]  Jianyong Ouyang,et al.  Highly conductive poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) films treated with an amphiphilic fluoro compound as the transparent electrode of polymer solar cells , 2012 .

[36]  DARRAN R. CAIRNS,et al.  Electromechanical Properties of Transparent Conducting Substrates for Flexible Electronic Displays , 2005, Proceedings of the IEEE.

[37]  Yang Yang,et al.  Dipole induced anomalous S-shape I-V curves in polymer solar cells , 2009 .

[38]  G. G. Stokes "J." , 1890, The New Yale Book of Quotations.

[39]  Peter Andersson,et al.  The Origin of the High Conductivity of Poly(3,4-ethylenedioxythiophene)−Poly(styrenesulfonate) (PEDOT−PSS) Plastic Electrodes , 2006 .

[40]  Byung-Kwan Yu,et al.  Fully spray-coated ITO-free organic solar cells for low-cost power generation , 2010 .

[41]  Brian J. Worfolk,et al.  Bulk Heterojunction Organic Photovoltaics Based on Carboxylated Polythiophenes and PCBM on Glass and Plastic Substrates , 2011 .

[42]  Ole Hagemann,et al.  A complete process for production of flexible large area polymer solar cells entirely using screen printing—First public demonstration , 2009 .

[43]  Yi Cui,et al.  Solution-processed metal nanowire mesh transparent electrodes. , 2008, Nano letters.

[44]  Peter Peumans,et al.  Smooth Nanowire/Polymer Composite Transparent Electrodes , 2011, Advanced materials.

[45]  F. Chen,et al.  High‐Conductivity Poly(3,4‐ethylenedioxythiophene):Poly(styrene sulfonate) Film and Its Application in Polymer Optoelectronic Devices , 2005 .

[46]  Zhenan Bao,et al.  Stretchable, elastic materials and devices for solar energy conversion , 2011 .

[47]  Martijn Kemerink,et al.  Conductivity, work function, and environmental stability of PEDOT:PSS thin films treated with sorbitol , 2008 .

[48]  Brian J. Worfolk,et al.  Indium tin oxide nanopillar electrodes in polymer/fullerene solar cells , 2011, Nanotechnology.

[49]  Frederik C. Krebs,et al.  Roll-to-roll fabrication of monolithic large-area polymer solar cells free from indium-tin-oxide , 2009 .

[50]  Alex K.-Y. Jen,et al.  Indium tin oxide-free semi-transparent inverted polymer solar cells using conducting polymer as both bottom and top electrodes , 2009 .

[51]  Wha-Tzong Whang,et al.  High-conductivity poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) film for use in ITO-free polymer solar cells , 2008 .

[52]  G. Crawford,et al.  Strain-dependent electrical resistance of tin-doped indium oxide on polymer substrates , 2000 .

[53]  Brett D. Martin,et al.  Towards a Transparent, Highly Conductive Poly(3,4‐ethylenedioxythiophene) , 2004 .

[54]  Paul Heremans,et al.  High‐Performance Organic Solar Cells with Spray‐Coated Hole‐Transport and Active Layers , 2011 .

[55]  Michael Niggemann,et al.  Organic solar cells using inverted layer sequence , 2005 .

[56]  Frederik C. Krebs,et al.  All solution roll-to-roll processed polymer solar cells free from indium-tin-oxide and vacuum coating steps , 2009 .

[57]  Brian J. Worfolk,et al.  Work Function Control of Interfacial Buffer Layers for Efficient and Air‐Stable Inverted Low‐Bandgap Organic Photovoltaics , 2012 .

[58]  Y. Kim,et al.  Highly Conductive PEDOT:PSS Electrode with Optimized Solvent and Thermal Post‐Treatment for ITO‐Free Organic Solar Cells , 2011 .

[59]  M. Kaltenbrunner,et al.  Ultrathin and lightweight organic solar cells with high flexibility , 2012, Nature Communications.

[60]  Jillian M. Buriak,et al.  Stable Inverted Polymer/Fullerene Solar Cells Using a Cationic Polythiophene Modified PEDOT:PSS Cathodic Interface , 2010 .

[61]  Y. H. Lo,et al.  Durability under mechanical bending of the indium tin oxide films deposited on polymer substrate by thermionically enhanced sputtering , 2010 .

[62]  Chunyue Pan,et al.  Performance improvement of polymer solar cells by using a solvent-treated poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) buffer layer , 2011 .

[63]  Sung-Hoon Choa,et al.  Mechanical flexibility of transparent PEDOT:PSS electrodes prepared by gravure printing for flexible organic solar cells , 2011 .

[64]  Michael D. McGehee,et al.  Conjugated Polymer Photovoltaic Cells , 2004 .

[65]  S. Chua,et al.  A mechanical assessment of flexible optoelectronic devices , 2001 .

[66]  Ronn Andriessen,et al.  ITO-free flexible organic solar cells with printed current collecting grids , 2011 .