The Role of Solvents’ Dielectric Constants in the Delicate Interplay between Microstructure and Optical Properties of Poly (3-Hexylthiophene) Thin Films
In order to gain a deeper understanding of the interplay between microstructure and functional properties of conducting polymers such as their optical behaviors, precise control of the structure formation methods of such polymers is of great importance. This work concerns the study of the role of solvents on the formation of different structures and how the resultant structural features affect the functional optical properties of a model Poly (3-hexylthiophene) conjugated system. Thin films of P3HT have been formed from solvents of different polarities and the structural features of the resultant films studied using optical microscopy and XRD technique. The photo-physical characteristics have been studied using UV-Vis spectroscopy and photoluminescence (PL) spectroscopy. We report that the nature of polymer structure and thus the resultant optical properties greatly depend on the solvent polarity and their dielectric constants rather than their solubility power. We have asserted that the solvent polarities have their fingerprints in the resultant film crystallinities, grain sizes, optical photoluminescence and the optical band gaps and by extension on the opto-electronic device applications.
Chirvase D, Chiguvare Z, Knipper M, Parisi J, Dyakonov V, Hummelen JC. Electrical and Optical design and characterization of regioregular poly(3-hexylthiophene-2,5diyl)/ fullerene-based heterojunction polymer solar cells. Synthetic Metals. 2003, 138:299-304
Jeffries E, McCullough RD. Conjugated polymers theory, synthesis, properties, and characterization, in regioregular polythiophenes. T.A.S.a.J.R. Reynolds, CRC Press, Taylor & Francis Group; 2007
Al-Ibrahim M, Roth H K, Schroedner M, Konkin A, Zhokhavets U, Gobsch G, Scharff P, Sensfuss, S. Organic Electronics. 2003, 6:65-71
Chang JF, Sun B, Breiby DW, Nielsen MM, Soelling TI, Giles M, McCulloch I, Sirringhaus H. Enhanced Mobility of Poly(3-hexylthiophene) Transistors by Spin-Coating from High-Boiling-Point Solvents. Chem Mater. 2004, 16:4772-4776
Osterbacka R, An CP, Jiang XM, Vardeny ZV. 2001, Synth Met. 116:317-323
Zhao K, Xue L, Liu J, Gao X, Wu S, Han Y, Geng Y. A new method to improve poly(3-hexyl thiophene) (P3HT) crystalline behavior: decreasing chains entanglement to promote order-disorder transformation in solution, Langmuir. 2010, 26:471-477
Chen CY, Chan SH, Li YJ, Wu KH, Chen HL, Chen JH, Huang WY, Chen SA. Formation and Thermally-Induced Disruption of Nanowhiskers in Poly(3-hexylthiophene)/Xylene Gel Studied by Small-Angle X-ray Scattering. Macromolecules. 2010, 43:7305-7311
Wu C, Wang X. Globule-to-Coil Transition of a Single Homopolymer Chain in Solution. Phys. Rev. Lett. 1998, 80:4092-4094.
Knaapila M, Garamus VM, Dias FB, Alma´sy L, Galbrecht F, Charas A, Morgado J, Burrows HD, Scherf U, Monkman AP. Structure and Dynamics of Nondilute Polyfluorene Solutions. Macromolecules. 2006, 39:6505-6512
Lim KC, Fincher CR. Heeger AJ. Rod-to-Coil Transition of a Conjugated Polymer in Solution. Phys. Rev. Lett. 1983, 50:1934-1937
Hu D, Yu J, Bachl B, Rossky PJ, Barbara PF. Solvent quality-induced nucleation and growth of parallelepiped nanorods in dilute poly(3-hexylthiophene) (P3HT) solution and the impact on the crystalline morphology of solution-cast thin film. Nature. 2000, 405:1030-1033
Gedde UW. Polymer Physics. New York: Chapman & Hall; 1995
Machui F, Langner S, Zhu XD, Abbott S, Brabec CJ. Determination of the P3HT:PCBM Solubility Parameters via a Binary Solvent Gradient Method: Impact of Solubility on the Photovoltaic Performance. Solar Energy Materials & Solar Cells. 2012, 100:138-146
Spano FC, Silva CH- and J-Aggregate Behavior in Polymeric Semiconductors. Annu. Rev. Phys. Chem. 2014, 65:477-500
Erb T, Gobsch G, Raleva S, Stühn B, Schilinsky P, Waldauf C, Brabec CJ. Correlation Between Structural and Optical Properties of Composite Polymer/Fullerene Films for Organic Solar Cells. Adv. Funct. Mater. 2005, 15, 1193
Kippelen B, Bredas J L. Organic photovoltaics. Energy Environ. Sci. 2009, 2:251-256
Grätzel M. Photoelectrochemical cells. Nature. 2001, 414:338-344
Heffner GW, Pearson DS. Molecular Characterization of. Poly(3-hexylthiophene). Macromolecules. 1991, 24:6295-6299
Zen A , Pflaum J, Hirschmann S, Zhuang W, Jaiser F, Asawapirom U, Rabe J B, Scherf U, Neher D, Adv Funct Mater. 2004, 14:757-764
Niles ET, PhD dissertation presented to Department of Chemistry, The University of New Mexico Albuquerque. New Mexico. 2013.
Spano FC. The Spectral Signatures of Frenkel Polarons in H- and J-Aggregates. Acc. Chem. Res. 2010, 43:429-439
Barnes MD, Baghar M. Journal of Polymer Science Part B: Polymer Physics.2012, 50:1121-1129
Niles ET, Roehling JD, Yamagata H, Wise AJ, Spano FC, Moule AJ, Grey JK. J-Aggregate Behavior in Poly-3-hexylthiophene Nanofibers. J. Phys. Chem. Lett. 2012, 3:259-263
Spano FC. Yamagata H. Vibronic Coupling in J-Aggregates and Beyond: A Direct Means of Determining the Exciton Coherence Length from the Photoluminescence Spectrum. J. Phys. Chem. B. 2011, 115:5133-5143
Spano FC. Modeling disorder in polymer aggregates: the optical spectroscopy of regioregular poly(3-hexylthiophene) thin films. J. Chem. Phys. 2005, 122:234701. Erratum. J. Chem. Phys. 2007,126:159901
Yamagata H, Spano FC. Interplay between intrachain and interchain interactions in semiconducting polymer assemblies: The HJ-aggregate model. The Journal of Chemical Physics. 2012, 136:184901
Green MA. Third generation photovoltaics: solar cells for 2020 and beyond. Physica: E-Low-Dimensional Systems & Nanostructures.2002, 65-70
Shrotriya V, Ouyang J, Tseng R. Absorption spectra modification in poly(3-hexylthiophene):methanofullerene blend thin films. Chemical Physics Letters. 2005, 411, 138-143
Ourida O, Mohammed B. Influence of the Blend Concentration of P3HT in the Performances of BHJ Solar Cells. Science Academy Transactions on Renewable Energy Systems Engineering and Technology (SATRESET). 2011:1-3
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