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Title: Conjugated Polymer Mesocrystals with Structural and Optoelectronic Coherence and Anisotropy in Three Dimensions
Abstract

Semiconducting mesocrystalline bulk polymer specimens that exhibit near‐intrinsic properties using channel‐die pressing are demonstrated. A predominant edge‐on orientation is obtained for poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) throughout 2 mm‐thick/wide samples. This persistent mesocrystalline arrangement at macroscopic scales allows reliable evaluation of the electronic charge‐transport anisotropy along all three crystallographic axes, with high mobilities found along the π‐stacking. Indeed, charge‐carrier mobilities of up to 2.3 cm2V−1s−1are measured along the π‐stack, which are some of the highest mobilities reported for polymers at low charge‐carrier densities (drop‐cast films display mobilities of maximum ≈10−3cm2V−1s−1). The structural coherence also leads to an unusually well‐defined photoluminescence line‐shape characteristic of an H‐aggregate (measured from the surface perpendicular to the materials flow), rather than the typical HJ‐aggregate feature usually found for P3HT. The approach is widely applicable: to electrical conductors and materials used in n‐type devices, such as poly{[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)} (N2200) where the mesocrystalline structure leads to high electron transport along the polymer backbones (≈1.3 cm2V−1s−1). This versatility and the broad applicability of channel‐die pressing signifies its promise as a straightforward, readily scalable method to fabricate bulk semiconducting polymer structures at macroscopic scales with properties typically accessible only by the tedious growth of single crystals.

 
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Award ID(s):
1729737
NSF-PAR ID:
10361847
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Materials
Volume:
34
Issue:
1
ISSN:
0935-9648
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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