Citation: Lei Sun, Jing-nan Zhao, Wei-heng Huang, Wen-hua Zhang, Liang-bin Li. Effect of Solution Concentration on Order-disorder Transition of Molecular Chains in Conjugated Polymer Solutions[J]. Acta Polymerica Sinica, ;2019, 50(8): 834-840. doi: 10.11777/j.issn1000-3304.2019.19023 shu

Effect of Solution Concentration on Order-disorder Transition of Molecular Chains in Conjugated Polymer Solutions

National Synchrotron Radiation Laboratory, Anhui Provincial Engineering Laboratory of Advanced Functional Polymer Film, University of Science and Technology of China, Hefei 230026

Corresponding author: Wen-hua Zhang, zhangwh@ustc.edu.cn
Received Date: 29 January 2019
Revised Date: 27 February 2019
Available Online: 17 April 2019

The concentration dependence of chain conformation and disorder-order transition of poly(3-hexylthiophene-2,5-diyl) (P3HT) in toluene solution at room temperature are investigated by multiple characterizations including photoluminescence spectroscopy (PL), UV-Vis absorption spectroscopy (UV-Vis), synchrotron radiation X-ray scattering technique (SAXS), and atomic force microscopy (AFM). The results indicate a critical concentration of ~ 5 mg/mL, at which the interchain interaction and chain aggregation state vary pronouncedly. In the dilute solution (< 5 mg/mL), P3HT chains maintain as independent random coils with negligible interchain interactions despite of regional segmental aggregate formation within the coils as revealed by PL and SAXS measurements. With the solution concentration exceeding the critical value of 5 mg/mL, the chain collapse takes place and the radius of gyration of the molecular chains decreases due to the strengthened π-π couplings among coils. The higher concentration of the solution leads to higher interchain entanglement and more local formation of rod-like segmental aggregates. The amount of the local segment aggregation is found to positively correlated with the concentration, while the radius of gyration and chain conformation exhibit nearly no variation any more at the concentrated solutions. SAXS data display a decreased power law of the concentrated solutions with respect to the dilute solutions, suggesting a lower dimension of the form factor and an improved interchain aggregation in the concentrated solution. This is in good agreement with the UV absorption and PL results. This concentration dependence of the regional chain disorder-order transition in P3HT/toluene solution is further verified to exert great influence on the final crystalline morphologies of the spin-casted films. The segmental aggregated orderings in solution can be effectively transferred to the thin films through namely the " memory effect” during the solution processing, resulting in nanowire structures and higher crystallinity of the films for the higher concentration solution.
- Conjugated polymer,
- Component concentration,
- Aggregation state,
- Chain conformation,
- Radius of gyration
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