Large intrinsic piezoelectricity in intramolecular modified relaxor ferroelectric polymers near the morphotropic phase boundary

• • Intrinsic d33 of -129.0 pC N-1 at 2.0 mol% DB content, surpassing prior MPB results (-63.5 pC N-1 for P(VDF-TrFE) and -69 pC N-1 with stretching) by >100%, enabling higher sensitivity in wearable sensors without poling fields. • • DB incorporation stabilizes long-range ferroelectric order and suppresses short-range relaxor behavior, as evidenced by structural and electrical characterization, providing a design rule for tuning phase boundaries in relaxor polymers. • • The dehydrochlorination reaction yields tunable DB content, with 2.0 mol% identified as the critical threshold for maximum piezoelectric response, offering a scalable synthesis route for industrial production. • • The enhanced intrinsic piezoelectricity eliminates the need for DC bias fields (previously required for d33 of -1050 pm V-1 in DB-modified P(VDF-TrFE-CFE)), simplifying device architecture and reducing power consumption in energy harvesting and actuation applications.