Increasing the Content of β Phase of Poly(9,9-dioctylfluorene) by Synergistically Controlling Solution Aggregation and Extending Film-forming Time

For poly(9,9-dioctylfluorene)(PFO),β phase (coplanar conformation with the intra-chain torsion angle of 165°) has a greater conjugation length and higher degree of order compared to those of α phase, which favors charge carrier transport. However, the highest content of β phase obtained so far is 45%. We propose to increase the content of β phase by promoting the solution aggregation of PFO molecules and extending film-forming time. For this purpose, 1,8-diiodooctane (DIO) is added to PFO o-xylene solution, which enhances the interaction of PFO chains and improves the planarity of PFO backbone, resulting in the formation of ordered aggregation. The aggregates act as nucleation centers to promote the formation of β phase. The content of β phase increases with increasing DIO concentration and reaches a platform of 39% as DIO is more than 4 vol%. Furthermore, the film is kept in a sealed environment with oxylene atmosphere for 3 h, thus the PFO molecules have enough time to diffuse to the crystallization front and achieve disorder-order transition. As a result, the crystallinity of PFO is improved significantly and the content of β phase increases to 52%, reaching the highest value reported so far.

Influence of bifurcation position and length of side chains on the structure of isoindigo-based conjugated polymer thin films

We chose a series of isoindigo-based conjugated polymer（ⅡDDT,ⅡDDT-C3 and ⅡDDT-C4） with different length of side chains and bifurcation positions to investigate the relationship between the degree of alignment and the length of side chains and bifurcation positions.We found that the dichroic ratio was increased from 2.37 to 5.23 when the side chain was longer and the bifurcation position was away from the backbone.The π-π stacking distance was decreased from 3.67 A to 3.61 A when the bifurcation position was away from the backbone because of its smaller hindrance and the d-spacing of the（100）was increased from 20.06 A to 25.21 A when the side chain was longer.All the polymers were adopted an edge-on orientation with the backbone paralleled with the long axis of fibers.The weak interaction of side-chain in ⅡDDT-C4 was beneficial for the molecules being rearranged in parallel during the contact line receding and the strong n-n interaction could accelerate the interchain assembly of the parallel molecules through π-π interaction to form aligned fibers.

To improve alignment of isoindigo-based conjugated polymer film by controlling contact line receding velocity

The macroscopic alignment of conjugated polymers with low grain boundary is essential to carrier transport. During film forming process, the match between contact line receding velocity and the critical alignment velocity is essential to get the alignment polymer film. In this paper, the contact line receding velocity of a D-A conjugated polymer film, isoindigo and bithiophene（IIDDT-C3）, was adjusted by solvent vapor content and film-formation temperature. Only when solvent vapor content was 0.3 m L and the film-formation temperature was 90C, the contact line receding velocity was in accordance with the critical alignment velocity, and the highest degree of alignment was attained in the IIDDT-C3 film, with the dichroic ratio up to 4.08. Fibers were aligned parallel with the direction of the contact line receding and the molecules of IIDDT-C3 adopted an edge-on orientation with the backbone parallel with the direction of fiber long axis. The p-p stacking distance between adjacent molecules was 3.63 ？.