Laser-Induced Periodic Surface Structures on Conjugated Polymers: Poly(3-hexylthiophene)

In this work, we report on the surface patterning of semiconducting poly(3-hexylthiophene) (P3HT) thin films by means of laser-induced periodic surface structures (LIPSS). Two different laser wavelengths, 266 and 532 nm, and a broad range of fluences and number of pulses have been used in order to optimize the LIPSS morphology. Ripples period and depth can be tuned by laser parameters. In particular, the high optical absorption of P3HT at 532 nm enables the formation of well-ordered nanostructures with periodicities around 460 nm. Near edge X-ray absorption fine structure (NEXAFS) and Raman spectroscopy reveal a good chemical stability of P3HT thin films during LIPSS formation. Conducting atomic force microscopy (C-AFM) performed on the LIPSS reveals a higher electrical conduction in the trenches than in the ridge regions. Resonance Raman spectroscopy and grazing incidence wide-angle X-ray scattering (GIWAXS) indicate a loss of crystallinity of P3HT thin films during LIPSS formation, suggesting melting of...

[1]  E. W. Meijer,et al.  Two-dimensional charge transport in self-organized, high-mobility conjugated polymers , 1999, Nature.

[2]  J. A. Pérez-Hernández,et al.  Ultraviolet and infrared femtosecond laser induced periodic surface structures on thin polymer films , 2012 .

[3]  C. McNeill,et al.  Simultaneous Surface and Bulk Imaging of Polymer Blends with X-ray Spectromicroscopy. , 2010, Macromolecular rapid communications.

[4]  Y. Aso,et al.  Synthesis and spectroscopic properties of a series of beta-blocked long oligothiophenes up to the 96-mer: revaluation of effective conjugation length. , 2003, Journal of the American Chemical Society.

[5]  K. Kanai,et al.  Effect of annealing on the electronic structure of poly(3-hexylthiophene) thin film. , 2010, Physical chemistry chemical physics : PCCP.

[6]  M. Toney,et al.  In situ measurement of power conversion efficiency and molecular ordering during thermal annealing in P3HT:PCBM bulk heterojunction solar cells , 2011 .

[7]  D. Bradley,et al.  The nature of in-plane skeleton Raman modes of P3HT and their correlation to the degree of molecular order in P3HT:PCBM blend thin films. , 2011, Journal of the American Chemical Society.

[8]  Y. Furukawa.  Electronic absorption and vibrational spectroscopies of conjugated conducting polymers , 1996 .

[9]  M. Castillejo,et al.  In situ monitoring of laser-induced periodic surface structures formation on polymer films by grazing incidence small-angle X-ray scattering. , 2015, Langmuir : the ACS journal of surfaces and colloids.

[10]  G. Shi,et al.  Raman Spectroscopic and Electrochemical Studies on the Doping Level Changes of Polythiophene Films during Their Electrochemical Growth Processes , 2002 .

[11]  Michael Olbrich,et al.  Proliferation of aligned mammalian cells on laser-nanostructured polystyrene. , 2008, Biomaterials.

[12]  T. Russell,et al.  P3HT nanopillars for organic photovoltaic devices nanoimprinted by AAO templates. , 2012, ACS nano.

[13]  Harald Ade,et al.  Miscibility, Crystallinity, and Phase Development in P3HT/PCBM Solar Cells: Toward an Enlightened Understanding of Device Morphology and Stability , 2011 .

[14]  A. Nogales,et al.  Poly(3-hexylthiophene) nanowires in porous alumina: internal structure under confinement. , 2014, Soft matter.

[15]  M. Thelakkat,et al.  Temperature and Molecular Weight Dependent Hierarchical Equilibrium Structures in Semiconducting Poly(3-hexylthiophene) , 2010 .

[16]  D. Ginger,et al.  Polymer nanowire/fullerene bulk heterojunction solar cells: how nanostructure determines photovoltaic properties. , 2010, ACS nano.

[17]  Volodimyr Duzhko,et al.  A Study on the Correlation Between Structure and Hole Transport in Semi‐Crystalline Regioregular P3HT , 2013 .

[18]  Varun Vohra,et al.  Organic solar cells based on nanoporous P3HT obtained from self-assembled P3HT:PS templates , 2012 .

[19]  C. Ting,et al.  Low-bandgap poly(thiophene-phenylene-thiophene) derivatives with broaden absorption spectra for use in high-performance bulk-heterojunction polymer solar cells. , 2008, Journal of the American Chemical Society.

[20]  K. Yager,et al.  Nanoimprint-induced molecular orientation in semiconducting polymer nanostructures. , 2011, ACS nano.

[21]  Ronald Österbacka,et al.  Spectroscopic Studies of Photoexcitations in Regioregular and Regiorandom Polythiophene Films , 2002 .

[22]  Donal D. C. Bradley,et al.  A strong regioregularity effect in self-organizing conjugated polymer films and high-efficiency polythiophene:fullerene solar cells , 2006 .

[23]  M. Castillejo,et al.  Assessment and formation mechanism of laser-induced periodic surface structures on polymer spin-coated films in real and reciprocal space. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[24]  H. Sirringhaus,et al.  Effect of interchain interactions on the absorption and emission of poly(3-hexylthiophene) , 2003 .

[25]  Dong Yun Lee,et al.  Poly(3‐hexylthiophene) Nanorods with Aligned Chain Orientation for Organic Photovoltaics , 2010 .

[26]  J. Grey,et al.  Resonance Raman overtones reveal vibrational displacements and dynamics of crystalline and amorphous poly(3-hexylthiophene) chains in fullerene blends. , 2013, The Journal of chemical physics.

[27]  Jenny Nelson,et al.  Morphology evolution via self-organization and lateral and vertical diffusion in polymer:fullerene solar cell blends. , 2008, Nature materials.

[28]  Tian-An Chen,et al.  Regiocontrolled Synthesis of Poly(3-alkylthiophenes) Mediated by Rieke Zinc: Their Characterization and Solid-State Properties , 1995 .

[29]  J. Grey,et al.  Resonance chemical imaging of polythiophene/fullerene photovoltaic thin films: mapping morphology-dependent aggregated and unaggregated C=C Species. , 2009, Journal of the American Chemical Society.

[30]  S. Wood,et al.  Understanding the relationship between molecular order and charge transport properties in conjugated polymer based organic blend photovoltaic devices. , 2013, The Journal of chemical physics.

[31]  Walter Hu,et al.  Nanoimprinted polymer solar cell. , 2012, ACS nano.

[32]  Jenny Clark,et al.  Role of intermolecular coupling in the photophysics of disordered organic semiconductors: aggregate emission in regioregular polythiophene. , 2007, Physical review letters.

[33]  M. Oujja,et al.  Pulsed laser deposition of polymers doped with fluorescent molecular sensors , 2006 .

[34]  E. Campaigne,et al.  Catalytic Reduction of 2-Acylthiophenes , 1951 .

[35]  Vishal Shrotriya,et al.  Absorption spectra modification in poly(3-hexylthiophene):methanofullerene blend thin films , 2005 .

[36]  C. Domingo,et al.  Physicochemical modifications accompanying UV laser induced surface structures on poly(ethylene terephthalate) and their effect on adhesion of mesenchymal cells. , 2014, Physical chemistry chemical physics : PCCP.

[37]  K. Yager,et al.  Nanostructured surfaces frustrate polymer semiconductor molecular orientation. , 2014, ACS nano.

[38]  Mukti Aryal,et al.  Nano-confinement Induced Chain Alignment in Ordered P3ht Nanostructures Defined by Nanoimprint Lithography High-density, and Ordered Nanostructures in Conjugated Polymer Poly(3-hexylthiophene) or P3ht, and Also to Simultaneously Control 3d Chain Alignment within These P3ht Nanostructures. Out-of-pla , 2022 .

[39]  Concepción Domingo,et al.  Assessment of femtosecond laser induced periodic surface structures on polymer films. , 2013, Physical chemistry chemical physics : PCCP.

[40]  C. Singh,et al.  Correlation of charge transport with structural order in highly ordered melt-crystallized poly(3-hexylthiophene) thin films , 2013 .

[41]  Jeong In Han,et al.  Enhancement of Field‐Effect Mobility Due to Surface‐Mediated Molecular Ordering in Regioregular Polythiophene Thin Film Transistors , 2005 .

[42]  M. Malfois,et al.  Recent experiments on a combined small- angle/wide-angle X-ray scattering beam line at the ESRF , 2003 .

[43]  Jiawang Zhou,et al.  Exciton Conformational Dynamics of Poly(3-hexylthiophene) (P3HT) in Solution from Time-Resolved Resonant-Raman Spectroscopy. , 2012, The journal of physical chemistry letters.

[44]  P. Rochon,et al.  Infrared-laser-induced periodic surface structure in azo-dye polymer , 2004 .

[45]  Yang Yang,et al.  High-efficiency solution processable polymer photovoltaic cells by self-organization of polymer blends , 2005 .

[46]  A. Zakhidov,et al.  Effects of nanostructure geometry on nanoimprinted polymer photovoltaics. , 2014, Nanoscale.

[47]  Juhwan Kim,et al.  Efficient Polymer Solar Cells with Surface Relief Gratings Fabricated by Simple Soft Lithography , 2008 .

[48]  Agnès Rivaton,et al.  The mechanism of photo- and thermooxidation of poly(3-hexylthiophene) (P3HT) reconsidered , 2009 .

[49]  M. Castillejo,et al.  Laser-induced periodic surface structures nanofabricated on poly(trimethylene terephthalate) spin-coated films. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[50]  R. Friend,et al.  Crystallization-Induced 10-nm Structure Formation in P3HT/PCBM Blends , 2013 .

[51]  Bo Li,et al.  Nanostructure dependence of field-effect mobility in regioregular poly(3-hexylthiophene) thin film field effect transistors. , 2006, Journal of the American Chemical Society.

[52]  J. Lüning,et al.  Calibrated NEXAFS spectra of common conjugated polymers. , 2011, The Journal of chemical physics.

[53]  P. Müller‐Buschbaum.  A Basic Introduction to Grazing Incidence Small-Angle X-Ray Scattering , 2009 .

[54]  R. Thomann,et al.  Semicrystalline morphology in thin films of poly(3-hexylthiophene) , 2004 .

[55]  Zhenan Bao,et al.  Soluble and processable regioregular poly(3‐hexylthiophene) for thin film field‐effect transistor applications with high mobility , 1996 .