25th anniversary article: high-mobility hole and electron transport conjugated polymers: how structure defines...

Area of Science:

• Materials Science
• Polymer Chemistry
• Organic Electronics

Background:

• Semicrystalline π-conjugated polymers exhibit significant charge-transport properties, making them crucial for organic electronic devices.
• Understanding the relationship between molecular structure and supramolecular organization is key to optimizing their performance.

Purpose of the Study:

• To investigate the structural organization of three distinct semicrystalline π-conjugated polymer families.
• To elucidate the factors driving supramolecular organization and their impact on charge-carrier mobility.
• To provide guidelines for designing polymers with enhanced supramolecular ordering.

Main Methods:

• Molecular mechanics and dynamics simulations utilizing re-parameterized force fields.
• Quantum-chemical calculations to determine intermolecular hopping transfer integrals.
• Analysis of the interplay between monomer unit characteristics and alkyl side chain packing.

Main Results:

• Supramolecular organization is dictated by the interplay between conjugated monomer unit properties and alkyl side chain packing.
• The degree of supramolecular organization directly impacts charge-carrier mobility.
• Specific structural features of poly(3-hexylthiophene) (P3HT), CDT-BTZ, and P(NDI2OD-T2) were analyzed.

Conclusions:

• The study provides a deeper understanding of structure-property relationships in conjugated polymers.
• Generic guidelines for designing advanced semiconducting polymers with tailored supramolecular structures are proposed.
• This work facilitates the development of high-performance organic electronic materials.