Surface-induced Microstructure and Performance Changes in P3HT Ultrathin Films

Hong-Tao Shan; Jia-Xin He; Bing-Yan Zhu; Xue-Ting Cao; Ying-Ying Yan; Jian-Jun Zhou; Hong Huo

doi:10.1007/s10118-024-3117-5

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Surface-induced Microstructure and Performance Changes in P3HT Ultrathin Films

RESEARCH ARTICLE | Updated：2024-05-11

- Surface-induced Microstructure and Performance Changes in P3HT Ultrathin Films
- Surface-induced Microstructure and Performance Changes in P3HT Ultrathin Films
- 高分子科学（英文版） 2024年42卷第6期页码：805-814
- Affiliations：
  
  Beijing Key Laboratory of Energy Conversion and Storage Materials, College of Chemistry, Beijing Normal University, Beijing 100875, China
- Author bio：
  
  hhuo@bnu.edu.cn
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (No. 21975029). A portion of this work is based on the data obtained at 1W1A, BSRF. The authors gratefully acknowledge the assistance of the beamline scientists at Diffuse X-ray Scattering Station (1W1A), BSRF during the experiments.;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-024-3117-5.
- DOI：10.1007/s10118-024-3117-5
  中图分类号：
- 纸质出版日期：2024-6-1，
  
  网络出版日期：2024-4-15，
  
  收稿日期：2024-1-18，
  
  修回日期：2024-2-22，
  
  录用日期：2024-3-1
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Shan, H. T.; He, J. X.; Zhu, B. Y.; Cao, X. T.; Yan, Y. Y.; Zhou, J. J.; Huo, H. Surface-induced microstructure and performance changes in P3HT ultrathin films. Chinese J. Polym. Sci. 2024, 42, 805–814

Hong-Tao Shan, Jia-Xin He, Bing-Yan Zhu, et al. Surface-induced Microstructure and Performance Changes in P3HT Ultrathin Films[J]. Chinese Journal of Polymer Science, 2024,42(6):805-814.
Shan, H. T.; He, J. X.; Zhu, B. Y.; Cao, X. T.; Yan, Y. Y.; Zhou, J. J.; Huo, H. Surface-induced microstructure and performance changes in P3HT ultrathin films. Chinese J. Polym. Sci. 2024, 42, 805–814 DOI： 10.1007/s10118-024-3117-5.

Hong-Tao Shan, Jia-Xin He, Bing-Yan Zhu, et al. Surface-induced Microstructure and Performance Changes in P3HT Ultrathin Films[J]. Chinese Journal of Polymer Science, 2024,42(6):805-814. DOI： 10.1007/s10118-024-3117-5.

摘要

The conductivity of the P3HT ultrathin films prepared on glass

Si wafers and ITO substrates was similar

yet the stretchability of P3HT ultrathin films on ITO substrate is better than that on the other two. The polar component of surface energy plays a critical role on the crystalline and morphology of P3HT ultrathin film

further determining its electronic and mechanical performances.

Abstract

In this work

poly(3-hexylthiophene) (P3HT) ultrathin films (P3HT-T) were prepared by spin-coating a dilute P3HT solution (in a toluene:

-dichlorobenzene (Tol:ODCB) blend with a volume ratio of 80:20) with ultrason

ication and the addition of the nucleating agent bicycle [2.2.1

]

heptane-2

3-dicarboxylic acid disodium salt (HPN-68L) on glass

Si wafers and indium tin oxide (ITO) substrates. The electrical and mechanical properties of the P3HT-T ultrathin films were investigated

and it was found that the conductivity and crack onset strain (COS) were simultaneously improved in comparison with those of the corresponding pristine P3HT film (P3HT-0

without ultrasonication and nucleating agent) on the same substrate

regardless of what substrate was used. Moreover

the conductivity of P3HT-T ultrathin films on different substrates was similar (varying from 3.7 S·cm

−1

to 4.4 S·cm

−1

)

yet the COS increased from 97% to 138% by varying the substrate from a Si wafer to ITO. Combining grazing-incidence wide-angle X-ray diffraction (GIXRD)

UV-visible (UV-Vis) spectroscopy and atomic force microscopy (AFM)

we found that the solid order and crystallinity of the P3HT-T ultrathin film on the Si wafer are highest

followed by those on glass

and much lower on ITO. Finally

the surface energy and roughness of three substrates were investigated

and it was found that the polar component of the surface energy

plays a critical role in determining the crystalline microstructures of P3HT ultrathin films on different substrates. Our work indicates that the P3HT ultrathin film can obviously improve the stretchability and simultaneously retain similar electrical performance when a suitable substrate is chosen. These findings offer a new direction for research on stretchable CP ultrathin films to facilitate future practical applications.

关键词

Keywords

P3HT ultrathin filmSubstrateCrystalline microstructuresPolar component of the surface energyElectrical and stretchable performances

references

Isono, T.; Ree, B. J.; Tajima, K.; Borsali, R.; Satoh, T. Highly ordered cylinder morphologies with 10 nm scale periodicity in biomass-based block copolymers.Macromolecules2018,51, 428−437..

Wang, X.; Zhu, Y.; Liu, Z.; Yuan, Y.; Qiu, L. Ultrathin polythiophene films prepared by vertical phase separation for highly stretchable organic field-effect transistors.Adv. Electron. Mater.2021,7, 2100591..

Zhang, F. L.; Johansson, M.; Andersson, M. R.; Hummelen, J. C.; Inganäs O. Polymer photovoltaic cells with conducting polymer anodes.Adv. Mater.2002,14, 662−665..

Cui, Y.; Yao, H.; Hong, L.; Zhang, T.; Xu, Y.; Xian, K.; Gao, B.; Qin, J.; Zhang, J.; Wei, Z.; Hou, J. Achieving over 15% efficiency in organic photovoltaic cellsviacopolymer design.Adv. Mater.2019,31, 1808356..

Zhang, Q.; Sun, Y.; Xu, W.; Zhu, D. Organic thermoelectric materials: emerging green energy materials converting heat to electricity directly and efficiently.Adv. Mater.2014,26, 6829−6851..

Fang, L.; Wei, M.; Barry, C.; Mead, J. Effect of spin speed and solution concentration on the directed assembly of polymer blends.Macromolecules2010,43, 9747−9753..

Roy, I.; Hazra, S. Structures of spin-coated and annealed monolayer and multilayer poly(3-dodecylthiophene) thin films.RSC Adv.2017,7, 2563−2572..

Negi, V.; Wodo, O.; van Franeker, J. J.; Janssen, R. A. J.; Bobbert, P. A. Simulating phase separation during spin coating of a polymer-fullerene blend: a joint computational and experimental investigation.ACS Appl. Energy Mater.2018,1, 725−735..

Yu, L.; Davidson, E.; Sharma, A.; Andersson, M. R.; Segalman, R.; Mueller, C. Isothermal crystallization kinetics and time-temperature-transformation of the conjugated polymer: poly(3-(2′-ethyl) hexylthiophene).Chem. Mater.2017,29, 5654−5662..

Jones, A. O. F.; Chattopadhyay, B.; Geerts, Y. H.; Resel, R. Substrate-induced and thin-film phases: polymorphism of organic materials on surfaces.Adv. Funct. Mater.2016,26, 2233−2255..

Xiao, M.; Jasensky, J.; Zhang, X.; Li, Y.; Pichan, C.; Lu, X.; Chen, Z. Influence of the side chain and substrate on polythiophene thin film surface, bulk, and buried interfacial structures.Phys. Chem. Chem. Phys.2016,18, 22089−22099..

Ji, D.; Xu, X.; Jiang, L.; Amirjalayer, S.; Jiang, L.; Zhen, Y.; Zou, Y.; Yao, Y.; Dong, H.; Yu, J.; Fuchs, H.; Hu, W. Surface polarity and self-structured nanogrooves collaboratively oriented molecular packing for high crystallinity toward efficient charge transport.J. Am. Chem. Soc.2017,139, 2734−2740..

Lee, W. H.; Cho, J. H.; Cho, K. Control of mesoscale and nanoscale ordering of organic semiconductors at the gate dielectric/semiconductor interface for organic transistors.J. Mater. Chem.2010,20, 2549−2561..

Kim, D. H.; Park, Y. D.; Jang, Y. S.; Yang, H. C.; Kim, Y. H.; Han, J. I.; Moon, D. G.; Park, S. J.; Chang, T. Y.; Chang, C. W.; Joo, M. K.; Ryu, C. Y.; Cho, K. W. Enhancement of field-effect mobility due to surface-mediated molecular ordering in regioregular polythiophene thin film transistors.Adv. Funct. Mater.2005,15, 77−82..

Skrypnychuk, V.; Boulanger, N.; Yu, V.; Hilke, M.; Mannsfeld, S. C. B.; Toney, M. F.; Barbero, D. R. Enhanced vertical charge transport in a semiconducting P3HT thin film on single layer graphene.Adv. Funct. Mater.2015,25, 664−670..

Kajiya, D.; Saitow, K. Ultrapure films of polythiophene derivatives are born on a substrate by liquid flow.ACS Appl. Energy Mater.2018,1, 6881−6889..

Patel, S. N.; Glaudell, A. M.; Peterson, K. A.; Thomas, E. M.; O'Hara, K. A.; Lim, E.; Chabinyc, M. L. Morphology controls the thermoelectric power factor of a doped semiconducting polymer.Sci. Adv.2017,3, e1700434..

Chen, Z.; Qin, S.; Jin, J.; Wang, Y.; Li, Z.; Luo, J.; Huang, H.; Wang, L.; Liu, D. Manipulating carrier concentration by self-assembled monolayers in thermoelectric polymer thin films.ACS Appl. Mater. Interfaces2021,13, 32067−32074..

Zhang, G.; McBride, M.; Persson, N.; Lee, S.; Dunn, T. J.; Toney, M.F.; Yuan, Z.; Kwon, Y.; Chu, P.; Risteen, B.; Reichmanis, E. Versatile interpenetrating polymer network approach to robust stretchable electronic devices.Chem. Mater.2017,29, 7645−7652..

Na, J. Y.; Kang, B.; Lee, S. G.; Cho, K.; Park, Y. D. Surface-mediated solidification of a semiconducting polymer during time-controlled spin-coating.ACS Appl. Mater. Interfaces2017,9, 9871−9879..

Kobayashi, T.; Uda, H.; Nagase, T.; Watanabe, M.; Matsukawa, K.; Naito, H. Correlation between the crystallization of polyfluorene and the surface free energy of substrates.Thin Solid Films2008,517, 1340−1342..

Jung, Y.; Kline, R. J.; Fischer, D. A.; Lin, E. K.; Heeney, M.; McCulloch, I.; DeLongchamp, D. M. The effect of interfacial roughness on the thin film morphology and charge transport of high-performance polythiophenes.Adv. Funct. Mater.2008,18, 742−750..

Kanai, K.; Miyazaki, T.; Suzuki, H.; Inaba, M.; Ouchi, Y.; Seki, K. Effect of annealing on the electronic structure of poly(3-hexylthiophene) thin film.Phys. Chem. Chem. Phys.2010,12, 273−282..

Shan, H.; Wang, Z.; He, J.; Zhu, B.; Cao, X.; Zhou, J.; Huo, H. A simple method to tailor the electrical and tensile properties of poly(3-hexylthiophene) ultrathin films.ACS Appl. Polym. Mater.2023,5, 8744−8753..

Zhang, X.; Liu, Y.; Ma, X.; Deng, H.; Zheng, Y.; Liu, F.; Zhou, J.; Li, L.; Huo, H. Sonocrystallization of poly(3-hexylthiophene) in a marginal solvent.Soft Matter2018,14, 3590−3600..

Shan, H.; He, J.; Zhu, B.; Zhou, J.; Huo, H. Synergistic effects of ultrasonication and the addition of a nucleating agent on improving the crystallization and performance of P3HT.Org. Electron.2023,114, 106733..

Yu, Z.; Niu, X.; Liu, Z.; Pei, Q. Intrinsically stretchable polymer light-emitting devices using carbon nanotube-polymer composite electrodes.Adv. Mater.2011,23, 3989−3994..

Zhang, Y.; Sheehan, C. J.; Zhai, J.; Zou, G.; Luo, H.; Xiong, J.; Zhu, Y. T.; Jia, Q. X. Polymer-embedded carbon nanotube ribbons for stretchable conductors.Adv. Mater.2010,22, 3027−3031..

Shabi, T.S.; Grigorian, S.; Brinkmann, M.; Pietsch, U.; Koenen, N.; Kayunkid, N.; Scherf, U. Enhancement in crystallinity of poly(3-hexylthiophene) thin films prepared by low-temperature drop casting.J. Appl. Polym. Sci.2012,125, 2335−2341..

Meredig, B.; Salleo, A.; Gee, R. Ordering of poly(3-hexylthiophene) nanocrystallites on the basis of substrate surface energy.ACS Nano2009,3, 2881−2886..

Brinkmann, M.; Contal, C.; Kayunkid, N.; Djuric, T.; Resel, R., Highly oriented and nanotextured films of regioregular poly(3-hexylthiophene) grown by epitaxy on the nanostructured surface of an aromatic substrate.Macromolecules 2010 ,43, 7604-7610..

Chang, J. F.; Sun, B. Q.; Breiby, D. W.; Nielsen, M. M.; Sölling, T. I.; 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..

Jin, S.; Hwang, J. H.; Lim, J. A.; Lee, E. Precrystalline P3HT nanowires: growth-controllable solution processing and effective molecular packing transfer to thin film.CrystEngComm2022,24, 1248−1257..

Baker, J. L.; Jimison, L. H.; Mannsfeld, S.; Volkman, S.; Yin, S.; Subramanian, V.; Salleo, A.; Alivisatos, A. P.; Toney, M. F. Quantification of thin film crystallographic orientation using X-ray diffraction with an area detector.Langmuir2010,26, 9146−9151..

Peng, Z.; Ye, L.; Ade, H., Understanding, quantifying, and controlling the molecular ordering of semiconducting polymers: from novices to experts and amorphous to perfect crystals.Mater. Horiz. 2022 ,9, 577-606..

Rivnay, J.; Noriega, R.; Kline, R. J.; Salleo, A.; Toney, M. F., Quantitative analysis of lattice disorder and crystallite size in organic semiconductor thin films.Phys. Rev. B 2011 ,84, 045203..

Huang, Y.; Tsao, C.; Chuang, C.; Lee, C.; Hsu, F.; Cha, H.; Chen, C.; Lin, T.; Su, C.; Jeng, U.; Su, W. Small- and wide-angle X-ray scattering characterization of bulk heterojunction polymer solar cells with different fullerene derivatives.J. Phys. Chem. C2012,116, 10238−10244..

Verploegen, E.; Miller, C. E.; Schmidt, K.; Bao, Z.; Toney, M. F. Manipulating the morphology of P3HT-PCBM bulk heterojunction blends with solvent vapor annealing.Chem. Mater.2012,24, 3923−3931..

Pei, D.; Wang, Z.; Peng, Z.; Zhang, J.; Deng, Y.; Han, Y.; Ye, L.; Geng, Y. Impact of molecular weight on the mechanical and electrical properties of a high-mobility diketopyrrolopyrrole-based conjugated polymer.Macromolecules2020,53, 4490−4500..

Boeckmann, M.; Schemme, T.; de Jong, D. H.; Denz, C.; Heuer, A.; Doltsinis, N. L. Structure of P3HT crystals, thin films, and solutions by UV/vis spectral analysis.Phys. Chem. Chem. Phys.2015,17, 28616−28625..

Urquhart, S. G.; Martinson, M.; Eger, S.; Murcia, V.; Ade, H.; Collins, B. A. Connecting molecular conformation to aggregation in P3HT using near edge X-ray absorption fine structure spectroscopy.J. Phys. Chem. C2017,121, 21720−21728..

Clark, J.; Silva, C.; Friend, R. H.; Spano, F. C., Role of intermolecular coupling in the photophysics of disordered organic semiconductors: aggregate emission in regioregular polythiophene.Phys. Rev. Lett. 2007 ,98, 206406..

Yuan, Y.; Shu, J.; Liu, P.; Zhang, Y.; Duan, Y.; Zhang, J. Study onπ-πinteraction in H-and J-aggregates of poly(3-hexylthiophene) nanowires by multiple techniques.J. Phys. Chem. B2015,119, 8446−8456..

Kim, D. H.; Jang, Y.; Park, Y. D.; Cho, K. Surface-induced conformational changes in poly(3-hexylthiophene) monolayer films.Langmuir2005,21, 3203−3206..

Stanfield, D. A.; Wu, Y.; Tolbert, S. H.; Schwartz, B. J. Controlling the formation of charge transfer complexes in chemically doped semiconducting polymers.Chem. Mater.2021,33, 2343−2356..

Chen, Y.; Yi, H. T.; Podzorov, V. High-resolution ac measurements of the hall effect in organic field-effect transistors.Phys. Rev. Appl.2016,5, 034008..

He, J.; Shan, H.; Zhu, B.; Zhou, J.; Huo, H. The importance of a good solvent of conjugated polymers for preparing dopant solution on the electrical and mechanical properties of sequentially doped conjugated polymer films.J. Mater. Chem. C2023,13, 6191−6201..

Scholes, D. T.; Yee, P. Y.; Lindemuth, J. R.; Kang, H.; Onorato, J.; Ghosh, R.; Luscombe, C. K.; Spano, F. C.; Tolbert, S. H.; Schwartz, B. J. The effects of crystallinity on charge transport and the structure of sequentially processed F4TCNQ-doped conjugated polymer films.Adv. Funct. Mater.2017,27, 1702654..

Zukiene, K.; Fataraite, E.; Jankauskaite, V. Estimation of the surface tension of VeoVa polymers and copolymers films.Polym. Chem. Technol.2009, 166−171..

Hugger, S.; Thomann, R.; Heinzel, T.; Thurn-Albrecht, T. Semicrystalline morphology in thin films of poly(3-hexylthiophene).Colloid Polym. Sci.2004,282, 932−938..

Ruffino, R.; Fichera, L.; Valenti, A.; Jankowski, M.; Konovalov, O.; Messina, G. M. L.; Licciardello, A.; Tuccitto, N.; Li-Destri, G.; Marletta, G. Tuning the randomization of lamellar orientation in poly(3-hexylthiophene) thin films with substrate nano-curvature.Polymer2021,230, 124071..

Destri, G. L.; Keller, T. F.; Catellani, M.; Punzo, F.; Jandt, K. D.; Marletta, G. Crystalline monolayer ordering at substrate/polymer interfaces in poly(3-hexylthiophene) ultrathin films.Macromol. Chem. Phys.2011,212, 905−914..

McCarthy, J. E.; Hanley, C. A.; Brennan, L. J.; Lambertini, V. G.; Gun'ko, Y. K. Fabrication of highly transparent and conducting PEDOT:PSS films using a formic acid treatment.J. Mater. Chem. C2014,2, 764−770..

Sethuraman, K.; Ochiai, S.; Yamada, Y.; Mototani, S.; Kojima, K.; Ohashi, A.; Mizutani, T. Third-harmonic generation of regioregular poly(3-hexylthiophene) thin films prepared using two solution methods.Jpn. J. Appl. Phys.2008,47, 450−454..

Aithal, P. S.; Nagaraja, H. S.; Rao, P. M.; Avasthi, D. K.; Sarma, A. Effect of high energy ion irradiation on electrical and optical properties of parahydroxy acetophenone.J. Appl. Phys.1997,81, 7526−7528..

Yi, Y.; Lyon, J. E.; Beerbom, M. M.; Schlaf, R. Characterization of indium tin oxide surfaces and interfaces using low intensity X-ray photoemission spectroscopy.J. Appl. Phys.2006,100, 093719..

Zhang, K.; Zhong, C.; Liu, S.; Mu, C.; Li, Z.; Yan, H.; Huang, F.; Cao, Y. Highly efficient inverted polymer solar cells based on a cross-linkable water-/alcohol-soluble conjugated polymer interlayer.ACS Appl. Mater. Interfaces2014,6, 10429−10435..

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