High‐Quality Nano/Micro Hairy Single Crystals Developed from Poly(3‐hexylthiophene)‐Based Conductive–Dielectric Block Copolymers Having Flat‐on and Edge‐on Orientations

Abstract

Highly uniform and conductive single crystals of poly(3‐hexylthiophene) (P3HT)‐based homo and block copolymers with the end coily blocks of polystyrene, poly(methyl methacrylate), and poly(ethylene glycol) are developed using self‐seeding method from varied quality solvents. Edge‐on and flat‐on orientations are detected depending on the thickness and width of single crystals. Coily blocks are excluded from the P3HT crystalline structures, leading to brush‐like or hairy regions on surface of grown single crystals in the longitude of P3HT chains. The larger single crystals possessing flat‐on orientation are obtained from weaker solvents at higher seeding temperatures. The longer P3HT chains are folded, however, the shorter backbones are laminated on each other. The highest backbone lamination occurs for homo‐P3HT7150 (Mn of P3HT = 7150 g mol−1) single crystals grown at 20 °C from anisole, the weakest employed solvent. In contract, highly ordered and folded hairy single crystals are acquired from better solvents and high molecular weight P3HTs. In these conditions, the crystallographic features of the hairy block copolymer single crystals are similar to those of nonhairy homo‐P3HT ones. The coily brush‐covered P3HT48 800 single crystals have more foldings compared to the homo‐P3HT48 800 ones, whereas only two laminated backbones in shorter P3HT blocks are detected.

Conjugated polymer single crystals and nanowires

“…This could explain why Cho et al and Reiter et al obtained P3HT single crystals with different orientations by using the same method. Using the self‐seeding method, P3AT or P3AT block copolymer single crystals have also been prepared by several groups …”

“…Using the self-seeding method, P3AT or P3AT block copolymer single crystals have also been prepared by several groups. [110][111][112] Using the appropriate methods, P3AT single crystals with different orientations have been prepared. The growth direction also depends on the growing conditions.…”

Enhanced properties of photovoltaic devices tailored with novel supramolecular structures based on reduced graphene oxide nanosheets grafted/functionalized with thiophenic materials

“…In a separate reactor, 10.0 g of anhydrous ferric chloride was dissolved in 30 mL of dried acetonitrile. This solution was slowly added to the reaction mixture with a rate of 5 mL min 21 under an argon atmosphere. The reaction mixture was refluxed for 24 h at room temperature under an inert atmosphere.…”

“…89 To verify the influence of pre-ordered supramolecules on improvement of the photovoltaic properties, four different designed hybrids (discussed thoroughly in previous sections) were used in the active layers. The PCE reached 0.97% when the P3HT/rGO supramolecules with face-on oriented P3HT chains were used in the active layer with the homo-P3HT 21,000 . Given that the charge transport in P3HT is anisotropic and is favored along the p-stacking direction, 90,91 the orientation of P3HT crystallites must affect the J sc .…”

Efficiency above 6% in poly(3‐hexylthiophene):phenyl‐C‐butyric acid methyl ester photovoltaics via simultaneous addition of poly(3‐hexylthiophene) based grafted graphene nanosheets and hydrophobic block copolymers

“…Among the conjugated polymers, regioregular P3HT (RR‐P3HT), thanks to appropriate processability and electrical properties, good function and a marked tendency to develop nanostructured crystals, is one of the attractive materials in electronic devices . The manipulation of the physical, thermal and optical characteristics of P3HT based systems and their application in photovoltaic cells has been reported in the literature. In organic solar cells, block copolymer compatibilizers were utilized to tune the active layer morphology .…”